TWI276646B - Catalyst for polymerization of polyester, polyester and process for preparing polyester - Google Patents
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1276646 五、發明說明（1) * 【技術領域】 本發明係關於一種聚酯聚合觸媒，聚酯及聚酯之製造方 法；更詳細地來說，本發明係關於一種可賦予改善成形時 過濾器阻塞等之聚酯聚合觸媒、聚酯、及其製造方法。 【背景技術】 聚酯，特別是聚對苯二甲酸乙二酯（以下，簡稱爲PET) ，其係具有優異的機械特性及化學特性而應用多種用途上 ，例如是應用在衣料用及產業資材用之纖維、包裝用及磁 性膠帶用等之各種薄膜或片材、瓶及工程塑膠等之成形物 〇 PET在工業上係藉由對酞酸或對酞酸二甲酯、與乙二醇 之酯化或酯交換以製造雙（2 -羥乙基）對酞酸酯，並於高溫 、真空下，利用觸媒使之聚縮合而得。聚縮合時所用的觸 媒，係廣泛地使用三氧化銻。雖然三氧化銻係一種具有便 宜、且優異的觸媒活性之觸媒，但是因爲在聚縮合時會析 出金屬銻，而不僅會使PET變黑，而且會產生異物等之問 題點。縱觀此等，常期盼一種完全不含銻、或不含以銻做 爲觸媒主成分之聚酯。 又，上述聚酯中之異物係會引起（例如）以下這樣的問題 〇 (1)在薄膜用之聚酯方面，金屬銻之出將成爲聚酯中之異 物，而於熔融押出時必然成爲污染模具之原因’並且 也是造成薄膜表面缺陷之原因。再者，在做爲中空成 1276646 五、發明說明（2) 形品等原料之情況下，亦將難以得到透明性優良的中 空成形品。 (2)纖維用聚酯中之異物，係爲造成纖維中強度變差之異 物，且是在製絲時污染模具、及過濾器之濾壓上昇之 原因。在製造聚酯纖維上，依照操作性爲主之觀點來 看，企盼求得一種不會產生異物之聚酯聚合觸媒。 曾經試著使用三氧化銻來做爲聚縮合觸媒，並且進行不 使PET變黑和產生異物之抑制。例如，專利第266 6 502號 ，藉由使用三氧化銻、鉍和硒之化合物來做爲聚縮合觸媒 ，以抑制PET中黑色異物之生成。又，特開平 9-291141 號述及：使用含有鈉及鐵之氧化物的三氧化銻來做爲聚縮 合觸媒，以抑制金屬銻之生成。然而，利用此等之聚縮合 觸媒，終究是無法達成降低銻含量之目的。 雖然曾經提議以鈦化合物、或錫化合物來做爲銻化合物 以外之聚縮合觸媒；但是用此等所製造的聚酯，於熔融成 形時易受熱而劣化，又且聚酯會有顯著的著色之問題點。 因此，嘗試著克服以鈦化合物來做爲聚縮合觸媒之問題 點；例如，特開55 - 1 1 6722號曾提議同時使用鈷鹽及鈣鹽 之四烷氧鈦酸鹽之方法。又，依照特開平 8 - 7358 1號， 則提議同時使用鈷化合物之四烷氧鈦酸鹽來做爲聚縮合觸 媒，以及使用螢光增白劑之方法。然而’根據此等技術’ 使用四烷氧鈦酸鹽來做爲聚縮合觸媒時’並無法使PET之 著色降低，亦無法達到抑制PET熱分解之效果。 1276646 五、發明說明（3) 銘化合物所知道的是觸媒活性差者。在錦化合物中，雖 然也有報告指出：與以其他的鋁化合物做爲聚縮合觸媒時 比較起來，利用鋁之螫合化合物時係具有更高的觸媒活性 ;但是不能說是比利用上述之銻化合物或鈦化合物時更具 有充分之觸媒活性；此外，使用以鋁化合物做爲聚縮合觸 媒時’則需要長時間來聚合聚酯，且其熱安定性及熱氧化 安定性也會變差等之問題點。又，使用以鋁化合物做爲聚 縮合觸媒時，會生成多量的對聚酯具不溶性之異物，於聚 酯成形時會由於該異物而引起過濾器阻塞；而且在以纖維 使用之際，於紡絲時常常會引起斷絲，又且使用時亦具有 薄膜物性等會變差等之問題。 一方面，依特公昭46-4103 1之揭示，其係發現··鹼金 屬或其化合物與鋁之螫合化合物共存時，會具有優良的觸 媒活性。依照該公報上所記載之方法聚合聚酯時，熱安定 性變優良，但會有熱氧化安定性依然不佳之問題；再者， 會生成多量的對聚酯具不溶性之異物，於聚酯成形時會由 於該異物而引起過濾器阻塞；而且在以纖維使用之際，於 紡絲時常常會引起斷絲，又且使用時亦具有薄膜物性等會 變差等之問題；因而不實用。 雖然也有在鋁化合物中添加鹼土類金屬化合物以使具有 充分的觸媒活性做成之觸媒的技術，但是爲使得到實用的 觸媒活性，則必須添加多量的鹼土類金屬化合物，此結果 將使得聚酯之熱安定性、熱氧化安定性變差，使得因加熱 1276646 五、發明說明（4) 之著色變大，對聚酯具不溶性異物之生成量也會變多。 雖然以鍺化合物做爲觸媒，能夠賦予具有銻化合物以外 之優良的觸媒活性，而且能夠提供無上述問題之聚酯，並 己經實用化了，但是此種觸媒也有所謂的非常貴之問題， 或者具有因在聚合中容易從反應系向外餾除，而使得反應 系之觸媒濃度發生變化，以致聚合變得難以抑制等課題； 並有使用來做爲觸媒主成分上之問題。 另外，抑制聚酯在熔融成形時的熱劣化之方法，舉例來 說，例如是從聚酯除去觸媒之方法。從聚酯除去觸媒之方 法，例如在特開平 1 0- 25 1 394號公報上，揭示了 一種於 酸性物質存在之下，使聚酯與超臨界流體之萃取劑接觸之 方法。但是，此種使用超臨界流體之方法，在技術上有困 難，以致製品之成本也會增加，因而不理想。 基於以上種種原由，乃期盼一種使用以銻及鍺之外的金 屬成分做爲觸媒的主要金屬成分之聚合觸媒，並優良之觸 媒活性，以及能賦予熔融成形時不會引起熱劣化、具優良 熱安定性之聚酯的聚合觸媒。 聚酯因熔融成形時之熱分解而使分子量降低，想必是熔 融成形口之耐熱性及力學特性下降之原因，由於熱分解之 副產物使得成形品之品質變差.，例如著色增加等。公知的 銻觸媒或鍺觸媒與其他的鈦觸媒比較起來，其係能夠提供 熔融成形時之熱安定性比較優良的聚酯；但熔融成形時熱 劣化依然是無法完全地防止。基此種種事由，乃期盼一種 1276646 五、發明說明（5) 能夠賦予在聚酯熔融成形時之熱劣化被極力地抑制的聚酯 之聚酯聚合觸媒。 W0 98/42769及特表平1 1 - 507694號等建議了一種以鋁 化合物做爲聚合觸媒之使用技術。可當做鋁化合物者，例 如是乙醯乙酸鋁等之鋁螫合化合物、氯化鋁或氫氧化鋁等 之無機酸鹽、羧酸之鋁鹽、或者是鋁烷氧化物等。其中， 乙醯乙酸鋁等之鋁螫合化合物，一般來說是貴的，而且因 化合物中鋁之含量降低，而使得成本增加之問題；或者具 有使對乙二醇等溶媒之溶解度變低之添加方法受到限制之 問題。氫氧化鋁或鋁烷氧化物等也具有對系統之溶解度變 低、觸媒活性下降之問題，或者有對聚酯具不溶性異物之 生成量也會變多的問題。含有氯化鋁等之氯的無機酸鹽， 雖然觸媒活性比較優良；但也具有對裝置之腐蝕性高的問 題，或者所得到的聚合物之著色變大等問題。 一方面，例如醋酸鋁、鹼基性醋酸鋁、乳酸鋁、苯甲酸 鋁等羧酸之鋁鹽，一般來說雖然是便宜、並對裝置之腐蝕 性低，但由於對聚酯之溶解性低，同時對觸媒之活性差， 因而不僅所製得的聚酯會有發生混濁之問題，而且做爲觸 媒使用時也會問題。例如，在特開平1 0 - 324747 1號上記 載著：用來做爲觸媒之醋酸鋁，係容易地形成對聚酯不溶 性之異物，並產生製絲性不良的問題。 本發明之目的係在於：提供一種經改良的聚酯及其製造 方法，其係使用以銻及鍺之外的金屬成分做爲觸媒的主要 1276646 五、發明說明（6 ) 金屬成分之聚合觸媒來製造聚酯，而且改善成形時過濾器 阻塞等之聚酯，及其製造方法。 本發明之另一目的係在於：提供一種使用以銻化合物及 鍺化合物之外的新穎聚合觸媒來製造聚酯之方法，以及藉 該方法所製造的聚酯。 本發明之其他目的係在於：提供一種不以含有銻化合物 及鍺化合物者來做爲觸媒主成分，觸媒活性優異，且在觸 媒之失活或沒有除去時，能賦予抑制在熔融成形時的熱劣 化效果，而得到熱安定性優良的聚酯之聚合觸媒。 本發明還提供一種使用前述之觸媒，來改善於進行薄膜 、瓶等之中空成形品、纖維、工程塑膠等之熔融成形時之 熱安定性，使用生樹脂、或再利用成形時所發生的碎屑均 可得到品質優良的製品之聚酯；以及使用前述聚酯聚合觸 媒以製造聚酯之方法。 本發明另外之目的係在於：提供一種能賦予熔融成形時 之熱劣化受到極力抑制這樣的聚酯之聚酯聚合觸媒，使用 前述之觸媒，使於進行薄膜、.瓶等之中空成形品、纖維、 工程塑膠等之熔融成形時之熱安定性顯著地改善，使用生 樹脂、或再利用成形時所發生的碎屑均可得到品質優良的 製品之聚酯；以及使用前述聚酯聚合觸媒以製造聚酯之方 法。 本發明之其他目的係在於：提供一種不以含有銻化合物 及鍺化合物者來命爲觸媒主成分，便宜、觸媒活性優異、 1276646 五、發明說明 ( 7) 對裝置之腐 蝕 少、更且能賦予降低對聚酯 不 溶 性異 物 之生 成的聚合觸 媒 ，及其製造方法。另外，本 發 明 也提 供 一種 使用前述觸 媒 以製造聚酯之方法，以及聚i 酯 〇 【發明之揭 示 ] 本發明人 等 基於解決上述課題之目的而 銳 意 地檢 討 ，結 果發現：使用 鹼金屬化合物、或鹼土金屬 化合 物、 與 鋁化 合物共存之 觸 媒進行聚合時所生成對聚酯 不 溶 性之 異 物的 起因，主要 係 由於鹼金屬化合物、或鹼土 金 屬 化合 物 所引 起的，更且 發 現藉由使聚酯中的鹼金屬化合 物 、或 驗 土金 屬化合物、 與 鋁化合物含量在特定之範圍 內 時 ，將 會 對於 生成對聚酯 不 溶性之異物具有抑制效果， 並 改 善聚 酯 成形 時過濾器阻 塞 等之問題，而完成本發明。 也就是說 ) 本發明提供一種可解決上述 課 題 之聚 酯 ，其 特徵在於： 該 聚酯係含有自鹼金屬及其化合 物 、和 鹼 土金 屬及其化合 物 所組成之群類中選出之至少 一 種 ,與 白 鋁及 其化合物所 組 成之群類中選出之至少一種 且 其含 量 係滿 足下述（1)及（2)式： (1)《M》 < 0.05 ； (2)《M》 / (A1» ^ 20 ； (式（1 )及 (2 )中，《Μ》係代表相對於聚 酯 中 酸成分計之 鹼金屬原子 和 1驗土金屬原子總合之旲耳％ 9 ( A1》 係代表 銘原子之莫 耳％) 〇 又，本發 明 人等基於解決上述課題之目 -9- 的而 銳意 地 檢討 1276646 五、發明說明（8) ，結果發現：使用鹼金屬化合物、或鹼土金屬化合物、與 鋁化合物共存之觸媒，係爲於聚合時會生成對聚酯不溶性 之異物的起因，更且進一步地檢討結果發現：與磷化合物 共存時會有降低異物之效果，另外發現藉由使聚酯中的上 述金屬化合物、或磷化合物含量在特定之範圍內時，將會 對於生成對聚酯不溶性之異物具有抑制效果，並改善聚酯 成形時過濾器阻塞等之問題，而達成本發明。 意即，本發明提供一種可解決上述課題之聚酯，其特徵 在於··該聚酯係含有自鹼金屬及其化合物、和鹼土金屬及 其化合物所組成之群類中選出之至少一種，與自鋁及其化 合物所組成之群類中選出之至少一種，以及自磷化合物所 組成之群類中選出之至少一種，且其含量係滿足下述 (4)〜（6)式： (4) 0.1 ^ [M] ^ 150 ；. (5) [M] / [A1] ^ 40 ； (6) [P] / [A1] ^ 0.01； (式（4)〜（6)中，[M]係代表聚酯中所含之鹼金屬原子 和鹼土金屬原子之總量（ppm) ; [A1]及[P]係分別代 表在聚酯中所含之鋁原子和磷原子之量（ppm))。 再者，本發明人等基於解決上述課題之目的而銳意地檢 討，結果發現：使用鹼金屬化合物、或鹼土金屬化合物、 與鋁化合物共存之觸媒，於聚合時會生成對聚酯不溶性之 異物，主要的起因係爲鹼金屬化合物、及鹼土金屬化合物 -10- 1276646 五、發明說明（9) ;更且進一步地檢討結果發現：在鹼金屬化合物、或鹼土 金屬化合物中使用含有自鋰、鈉、鉀、鈹、鎂、鈣及其化 合物所組成之群類中選出之至少一種’而且其在聚酯中的 含量在特定之範圍內，更且與磷化合物共存時會有降低異 物生成之效果，並改善聚酯成形時過濾器阻塞等之問題’ 而達成本發明。 意即，本發明解決上述課題之方法，係提供一種聚酯及 其製造方法，其特徵在於··該聚酯係含有自鋰、鈉、鉀、 鈹、鎂、鈣及其化合物所組成之群類中選出之至少一種’ 與自鋁及其化合物所組成之群類中選出之至少一種，以及 自磷化合物所組成之群類中選出之至少一種，且鋰、鈉、 鉀、敏、鎂、15及其化合物之總含量，以換算成金屬原子 計，每106克之聚合物係在7.0莫耳以下。 又，本發明人等基於解決上述課題之目的而銳意地 檢討，結果發現：一種使用主要金屬成分爲鋁化合物 的觸媒所製造而成的聚酯，而且含有自磷化合物構成 群類中選出之至少一種以及含有自苯酚系化合物構成 群類中選出之至少一種，更且磷原子和鋁原子之含量 比在特定範圍賽之聚酯，係爲可以改善成形時之過濾 器阻塞之問題及熱氧化安定性之物，而達成本發明。 意即，本發明解決上述課題之方法，係提供一種聚 酯及其製造方法，其特徵在於：該聚酯係含有自鋁及 其化合物所組成之群類中選出之至少一種，與自磷化 -11- 1276646 五、發明說明（1〇) 合物所組成之群類中選出之至少一種，以及自苯酚系 化合物所組成之群類中選出之至少一種，且該聚酯中 磷原子之含量（ppm)、和鋁原子之含量（ppm)的比値係 在0.01〜50之範圍。 另外，本發明人等基於解決上述課題之目的而銳意地檢 討，結果發現：使用鋁化合物做成之觸媒於聚合時會生成 對聚酯不溶性之異物的起因，主要係爲鋁化合物；更且進 一步地檢討結果發現：在聚酯中鋁化合物與磷化合物共存 ，而且鋁化合物與磷化合物之含量成特定比値時，會有降 低異物之效果，並改善聚酯成形時過濾器阻塞等之問題， 而達成本發明。 意即，本發明解決上述課題之方法，係提供一種聚酯， 其特徵在於：該聚酯係含有自鋁及其化合物所組成之群類 中選出之至少一種，與自磷化合物所組成之群類中選出之 至少一種，且該聚酯中磷原子之含量（ppm)、和銘原子之 含量（ppm)的比値係在0.5〜20之範圍。 又，本發明提供一種使用上述金屬及/或化合物做成的 觸媒所製造的上述聚酯，及其製造方法。 再者，本發明人等基於解決上述課題之目的而銳意地檢 討，結果發現：雖然鋁化合物的觸媒活性較差，但藉由與 磷化合物組合以做爲觸媒時，將可得到充分的活性，因而 達成本發明。使用本發明之聚合觸媒時，將可便宜地得到 不使用銻化合物之品質優良的聚酯。 -12- 1276646 五、發明說明（11) 意即，本發明解決上述課題之方法，係提供一種聚酯之 製造方法，其特徵在於：在製造聚酯時，添加自鋁及其化 合物所組成之群類中選出之至少一種，與自磷化合物所組 成之群類中選出之至少一種，且所添加的磷原子、和鋁原 子之比値係在0.5〜20之範圍；以及提供一種藉由該方法 所製造之聚酯。又，本發明提供一種聚合聚酯觸媒，其特 徵在於：該聚酯係由自鋁及其化合物所組成之群類中選出 之至少一種，與自磷化合物所組成之群類中選出之至少一 種所構成，且磷原子、和鋁原子之比値係在上述之範圔； 及提供使用其所製造之聚酯，以及聚酯之製造方法。 此外，本發明人等基於解決上述課題之目的而銳意地檢 討，結果發現：雖然金屬或金.屬化合物本身的觸媒活性較 差，但使之與磷化合物組合可使成爲觸媒活性增加之聚酯 聚合觸媒，從而發現觸媒活性優良之由金屬、金屬化合物 、及磷化合物所成之聚酯聚合觸媒，並且是一種在觸媒之 失活或沒有除去時，能賦予抑制在熔融成形時的熱劣化效 果，而得到熱安定性優良的聚酯之聚合觸媒，而完成本發 明。 也就是說，本發明解決上述課題之方法，係提供一種聚 酯聚合觸媒，其特徵在於··該聚酯聚合觸媒係由金屬或金 屬化合物、與磷化合物所構成，且活性參數（AP)滿足下述 (10)式； (10) AP (分）< APX (分）； -13- 1276646 五、發明說明（12) (上述式中，AP係代表使用預定量之觸媒，在275 °C、 0 . 1托利之減壓度下，聚合特性黏滯度爲0.65 dl/克之 聚對苯二甲酸乙二酯（PET)所需要的時間（分）；APX係代表 只有上述金屬或金屬化合物時，在與上述同樣的用量、同 樣的條件下聚合PET所需要的時間（分））。 另外，本發明提供一種聚酯聚合觸媒，其特徵在於：該 聚酯聚合觸媒係用於聚合具有熱安定性參數（TS )滿足下述 (9)式之聚對苯二甲酸乙二酯（PET)。由使用該聚酯聚合觸 媒聚合之聚酯所形成的薄膜、瓶等之中空成形品、纖維、 工程塑膠等之熔融成形時之熱安定性，將可得到顯著的改 善，而且使用生樹脂、或再利用成形時所發生的碎屑均可 得到品質優良的製品。 (9) TS < 0.20 ； (上述式中，TS爲將1克之特性黏滯度（[IVh )爲 0.64〜0.66 dl/克之PET放入試驗管中，以130°C真空乾 燥12小時之後，在不流通之氮氣氛圍氣下，在300°C維持 熔融2小時後，以下式來計算特性黏滯度（[IV]f )之數 値）； TS = 0.245 { [IV]，1.47 - [IVh·1.47} 特性黏滯度爲0.64〜0.66 dl /克之PET，實際上係 可預先測定PET聚合反應容器之攪拌扭矩、與特性黏滯度 之相關性，以管理聚合狀態之攪拌扭矩，藉由使攪拌扭矩 達到預定値時令聚合停止而得到。 -14- 1276646 五、發明說明（13) 又，本發明人等基於提高羧酸鋁鹽之觸媒活性目的而銳 意地檢討，結果發現：使用預先將羧酸之鋁鹽溶解在水或 有機溶劑中之物所做成的觸媒，將可使得觸媒活性增加， 而得到本發明之建議案。 也就是說，本發明解決上述課題之方法，係提供一種聚 酯聚合觸媒，其特徵在於：該聚酯聚合觸媒係將由羧酸鋁 鹽所組成之群類中選出之至少一種，予以溶解在水及/或 有機溶媒中形成之溶液所構成；以及提供一種製造該溶液 之方法。 【實施發明之最佳具體實施例】 本發明之聚酯必須是含有自鹼金屬及其化合物、和鹼土 金屬及其化合物所組成之群類中選出之至少一種；相對於 聚酯中二羧酸及多元羧酸等之羧酸成分的全部構成單位之 莫耳數計，金屬原子之總含量係少於〇·〇5莫耳％。又，較 宜是在0.005莫耳％以上。當含量係在0.05莫耳％以上時 ，會生成多量的對聚酯不溶性之異物，結果在紡絲時頻繁 地發生斷絲、或成形時引起所謂的過濾器阻塞等問題。又 ，樹脂會顯著地著色，而破壞成形品外觀等問題，也會發 生樹脂之耐加氫分解性變差之問題。當含量比0.005莫耳 %少時，將會發生樹脂之熱安定性缺乏之問題，同時在使 用來做爲觸媒的情況下，觸媒活性會顯著地下降；因而不 佳。比較好的含量範圍係從0.008莫耳％至0.03莫耳％ ; 更宜是在0.01莫耳％到0.02莫耳％之範圍。 -15- 1276646 五、發明說明（14) 本發明之聚酯必須是含有自鹼金屬及其化合物、和鹼土 金屬及其化合物所組成之群類中選出之至少一種上，添加 自鋁及其化合物所組成之群類中選出之至少一種。又，相 對於自鹼金屬及其化合物、和鹼土金屬及其化合物所組成 之群類中選出之至少一種，與自鋁及其化合物所組成之群 類中選出之至少一種之含量計，鹼金屬原子和鹼土金屬原 子之總量，與鋁原子之莫耳比必須是在20以下。又，較 宜是0.1以上。當比値係超過20時，會生成多量的對聚 酯不溶性之異物，結果在紡絲時頻繁地發生斷絲、或成形 時引起所謂的過濾器阻塞等問題。又，在使用來做爲觸媒 的情況下，會發生所謂的觸媒活性會顯著地下降之問題。 當比値小於0 · 1時，會生成多量的因鋁化合物所引起的對 聚醋不溶性之異物’又且樹脂之熱安定性會變差，因而不 佳。比値之較好的範圍係從0 . 5至1 0。 當使聚酯中之自鹼金屬及其化合物、和鹼土金屬及其化 合物所組成之群類中選出之至少一種，與自銘及其化合物 所組成之群類中選出之至少一種之含量在上述範圍時，將 具有對聚酯不溶性之異物發生抑制效果，並改善在紡絲時 斷絲、或成形時過濾器阻塞等問題。 又’本發明之鋁及其化合物之含量，相對於聚酯中二羧 酸及多元羧酸等之羧酸成分的全部構成單位之莫耳數計， 鋁原子含量較宜是在從0.001莫耳％到〇 〇5莫耳％之範圍 。當鋁原子含量係超過0 · 05莫耳％時，所生成的聚酯之熱 -16- 1276646 五、發明說明（15) 安定會變差，因而不佳。當鋁原子含量係在0.001莫耳％ 以下時，在使用來做爲觸媒的情況下，觸媒活性會顯著地 下降，因而不宜。比較好的含量範圍係從0.005莫耳％至 0·04莫耳％ ;更宜是在0.01莫耳％到0.03莫耳％之範圍。 依照減低異物之觀點來看，本發明之聚酯所含有的鹼金 屬原子、和鹼土金屬原子之總量，宜是在25 ppm以下。 此含量較宜是在20 ppm以下，更宜是在15 ppm以下。 又，在本發明之聚酯中，雖然是必須是含有上述之自鹼 金屬及其化合物、和鹼土金屬及其化合物所組成之群類中 選出之至少一種；但是其中，由於含有鹼土金屬及其化合 物之聚酯，其熱安定性比較差，因加熱而大量地著色，異 物產生量也比較多；所以在本發明之聚酯中，較宜是不含 有鹼土金屬及其化合物、但含有鹼金屬。 另外，本發明之聚酯較宜是含有磷化合物。因爲含有磷 化合物時，可得到抑制由鹼金屬、或鹼土金屬而來之異物 的效果，同時並改善聚酯之熱安定性。 根據以上所述，含有之鋁及其化合物、和鹼土金屬及其 化合物之聚酯，雖然熱安定性有變差的傾向，異物之生成 也比較多；但使含有在本發明範圍之鹼土金屬，更且含有 磷化合物時，將可改善聚酯之熱安定性及異物之問題。 依照本發明之方法，在製造聚酯時添加磷化合物時，將 會具有抑制生成對聚酯不溶性的異物之效果，因而較理想 。又，因添加磷化合物’可使得聚酯之熱安定性等提高’ -17- 1276646 五、發明說明（1 6 ) 從而較爲理想。 本發明之磷化合物之使用量，相對於聚合所得聚酯中的 二羧酸及多元羧酸等之羧酸成分的全部構成單位之莫耳數 計，較宜是在從5 X 10·5莫耳％到1莫耳％之範圍；更宜 是在從1 X 1〇·4莫耳％到0.5莫耳％之範圍。 又，本發明之另外的聚酯，必須是含有自鹼金屬及其化 合物、和鹼土金屬及其化合物所組成之群類中選出之至少 一種；在聚酯中金屬原子之總含量係在0 . 1 ppm以上 150ppm以下。當含量多於150 ppm時，會生成多量的對聚 酯不溶性之異物，結果在紡絲時頻繁地發生斷絲、或成形 時引起所謂的過濾器阻塞等問題。又，會產生樹脂之著色 會變得顯著，破壞成形品外觀之問題，及樹脂之熱安定性 、耐加氫分解性下降之問題。當含量比0.1 ppm少時，會 發生樹脂之熱安定性缺乏之問題。在使用來做爲觸媒的情 況下，會發生所謂的觸媒活性會顯著地下降之問題。比較 好的含量範圍係在1 ppm以上100 ppm以下；更宜是在 5 ppm以上50 ppm以下。 本發明之聚酯必須是含有上述自鹼金屬及其化合物、和 鹼土金屬及其化合物所組成之群類中選出之至少一種上， 添加自鋁及其化合物所組成之群類中選出之至少一種。又 ，相對於自鹼金屬及其化合物、和鹼土金屬及其化合物所 組成之群類中選出之至少一種，與自鋁及其化合物所組成 之群類中選出之至少一種之含量計，鹼金屬原子和鹼土金 -18- 1276646 五、發明說明（17) 屬原子之總量（ppm)，與鋁原子之含量（ppm)比値必須是在 40以下。又，該比値較宜是0.05以上。當比値係超過40 時，會生成多量的對聚酯不溶性之異物，結果在紡絲時頻 繁地發生斷絲、或成形時引起所謂的過濾器阻塞等問題。 又，在使用來做爲觸媒的情況下，會發生所謂的觸媒活性 會顯著地下降之問題。當比値小於〇.〇5時，會生成多量 的因鋁化合物所引起的對聚酯不溶性之異物，又且樹脂之 熱安定性會變差，因而不佳。比値之較好的範圍係在0 . 1 以上20以下，更宜是在0.5以上10以下。 本發明之聚酯必須是含有上述自鹼金屬及其化合物、和 鹼土金屬及其化合物所組成之群類中選出之至少一種，及 自鋁及其化合物所組成之群類中選出之至少一種上，添加 自磷及其化合物所組成之群類中選出之至少一種。又，相 對於自鹼金屬及其化合物、和鹼土金屬及其化合物所組成 之群類中選出之至少一種，與自鋁及其化合物所組成之群 類中選出之至少一種之含量計，磷原子含量（ppm)與鋁原 子含量（ppm)之比値必須是在0.01以上。又，該比値較 宜是30以下。當比値小於0 · 01時，會生成多量的因鋁化 合物所引起的對聚酯不溶性之異物，又且樹脂之熱安定性 會變差，因而不佳。當比値係超過30時，會生成多量的 對聚酯不溶性之異物；又，在使用來做爲觸媒的情況下， 會發生所謂的觸媒活性會顯著地下降之問題。比値之較好 的範圍係在0 · 1以上20以下，更宜是在1以上1 〇以下。 -19- 1276646 五、發明說明（18) 在本發明之聚酯中，藉由使含有自鹼金屬及其化合物、 和鹼土金屬及其化合物所組成之群類中選出之至少一種， 及自鋁及其化合物所組成之群類中選出之至少一種，以及 自磷及其化合物所組成之群類中選出之至少一種；將會具 有抑制生成對聚酯不溶性的異物之效果，可改善在紡絲時 斷絲、或成形時過濾器阻塞等問題。 又，就在本發明聚酯中之鋁及其化合物而言，其在聚酯 中所含有的鋁原子之範圍，較理想是在0.5ppm以上 500ppm以下者。當鋁原子之含量超過500 ppm時，會生成 多量的對聚酯不溶性之異物，發生樹脂之熱安定性缺乏之 問題，因而不佳。當鋁原子含量少於0.5ppm時，會生多 量的起因於鹼金屬及鹼土金屬之異物，在使用來做爲觸媒 的情況下，會發生觸媒活性顯著下降，因而不宜。比較好 的含量範圍係在5 ppm以上70 ppm以下；更宜是在 lOppm以上30 ppm以下。 又，就在本發明之磷化合物而言，在聚酯中磷原子之含 量範圍較宜是在1 ppm以上lOOppm以下。當磷原子含量 少於1 ppm時，會缺乏對生成聚酯不溶性異物之抑制效果 ，又聚酯之熱安定性會變差，因而不佳。當磷原子之含量 超過1 000 ppm時，會生多量的聚酯不溶性之異物，因而 不宜。比較好的含量範圍係在 10 ppm以上 200 ppm以 下；更宜是在20 ppm以上100 ppm以下。 在本發明之聚酯中，雖然必須含有自鹼金屬及其化合物 -20- 1276646 五、發明說明（19) 、和鹼土金屬及其化合物所組成之群類中選出之至少一種 ，與自鋁及其化合物所組成之群類中選出之至少一種，但 依照減低聚酯中之異物，以及減低聚酯著色之觀點來看， 彼等之中較宜是含有自鋰、鈉、鉀、鈹、鎂、鈣及其化合 物所組成之群類中選出之至少一種。彼等之中含有自鋰、 鈣及其化合物所組成之群類中選出之至少一種者，因會具 有優良的聚酯熱安定性而較佳。更且，依照減低聚酯著色 之觀點來看，較宜是含有自鈣及其化合物所組成之群類中 選出之至少一種者。 本發明係關於一種使用上述金屬及/或化合物做成之觸 媒所製得之聚酯、及其製造方法。所添加的金屬及/或化 合物之量，必須是使在最終所得到的聚酯中之金屬原子含 量如上述者。藉以該方法所製得的聚酯，係爲一種經改善 對生成聚酯不溶性異物之抑制效果，紡絲時斷絲、或成形 時過濾器阻塞之問題者。 在本發明中所使用來做爲聚合觸媒之鹼金屬及其化合物 、和鹼土金屬及其化合物，較宜是自Li、Na、K、Rb、Cs 、Be、Mg、Ca、Sr、Ba中所選取的至少一種；其中使用鹼 金屬及其化合物者，由於會減低對聚酯不溶性之異物，聚 酯之熱安定性也優良，因而較理想。在使用鹼金屬及其化 合物的情況下，較宜是使用Li、Na、K及其化合物。此等 之中，爲使對聚酯不溶性之異物減低，更宜是使用Li及 其化合物。 -21 - 1276646 五、發明說明（2〇) 又，本發明之另一種聚酯的特徵係在於··含有自鋰、鈉 、鉀、鈹、鎂、鈣及其化合物所組成之群類中選出之至少 一種’及自鋁及其化合物所組成之群類中選出之至少一種 ’以及自磷及其化合物所組成之群類中選出之至少一種； 而且鋰、鈉、鉀、鈹、鎂、鈣及其化合物之總含量，以換 算成金屬原子計，每106克之聚合物係在7.0莫耳以下。 當該含量係多於7 · 0莫耳時，會生成多量的對聚酯不溶性 之異物，結果在紡絲時頻繁地.發生斷絲、或成形時引起所 謂的過濾器阻塞等問題。又，樹脂會顯著地著色，而破壞 成形品外觀等問題，也會發生榭脂之耐加氫分解性變差之 問題。該含量較宜是在0.05莫耳以上；當含量比這個少 時，將會發生樹脂之熱安定性缺乏之問題，又在使用來做 爲觸媒的情況下，觸媒活性會顯著地下降。比較好的含量 範圍係0.1〜4.0莫耳；更宜是0.2〜2. 5莫耳；特別理 想的是 0 . 2〜1 . 2莫耳。此種聚酯係爲一種經改善對生 成聚酯不溶性異物之抑制效果，紡絲時斷絲、或成形時過 濾器阻塞之問題者。 在本發明聚酯中鋁及其化合物之含量，以鋁原子計較理 想是0.5〜500 ppm。當銘原子之含量超過500 ppm時， 不僅會生成多量的起因於鋁原子之對聚酯不溶性異物，而 且會發生樹脂之熱安定性缺乏之問題，因而不佳。當鋁原 子含量少於0.5 ppm時，會生多量的起因於鹼金屬及鹼土 金屬之異物，而且在使用來做爲觸媒的情況下，會發生觸 -22- 1276646 五、發明說明（21 ) 媒活性顯著下降，因而不宜。比較好的含量範圍係在 5〜70ppm ;更宜是在10〜40 ppm之範圍；特別好的是在 1 5〜25 ppm之範圍。 在本發明聚酯中磷及其化合物之含量，以磷原子計較理 想是1〜1000 ppm。當磷原子含量少於1 ppm時，不僅會 缺乏抑制生成對聚酯不溶性異物之效果，而且樹脂之熱安 定性會降低，因而不佳。當磷原子之含量超過1 000 ppm 時，會生成多量的起因於鋁原子之對聚酯不溶性異物，因 而不宜。比較好的含量範圍係在10〜200 ppm ;更宜是在 20〜100 ppm之範圍。 在本發明之聚酯中，雖然必須含有自鋰、鈉、鉀、鈹、 鎂、鈣及其化合物所組成之群類中選出之至少一種；但依 照減低聚酯中之異物，以及減低聚酯著色之觀點來看，彼 等之中以含有自鋰、鈉、鎂、鈣及其化合物所組成之群類 中選出之至少一種者較爲理想。彼等之中，較宜是含有自 鋰、鈉及其化合物所組成之群類中選出之至少一種者。 本發明係關於一種使用觸媒來製造聚酯之方法，其中所 使用的觸媒係含有自鋰、鈉、鉀、鈹、鎂、鈣及其化合物 所組成之群類中選出之至少一種，以及自鋁及其化合物所 組成之群類中選出之至少一種，而且其含量相對於最終所 得到的聚酯計係在上述範圍。以該方法所得到之聚酯，係 爲一種經改善對生成聚酯不溶性異物之抑制效果，紡絲時 斷絲、或成形時過濾器阻塞之問題者。 -23- 1276646 五、發明說明（22) 又，本發明之另一種聚酯，其係含有自鋁及其化合物所 組成之群類中選出之至少一種，與自磷化合物所組成之群 類中選出之至少一種，以及自苯酚系化合物所組成之群類 中選出之至少一種之聚酯；而且在該聚酯中所含磷原子之 量（ppm)、和鋁原子之量（ppm)的比値（磷原子量/鋁原子量） 係在0.01〜50之範圍。當磷原子之量（ppm)、和鋁原子之 量（ppm)的比値（磷原子量/鋁原子量）係比0.01小時；會 生成多量的對聚酯不溶性之異物，結果在紡絲時頻繁地發 生斷絲、或成形時引起所謂的過濾器阻塞等問題。又，樹 脂會顯著地著色，而破壞成形品外觀等問題，也會發生樹 脂之耐加氫分解性變差之問題。在該比値超過50的情形 下，會生成多量的對聚酯不溶性之異物，結果在紡絲時頻 繁地發生斷絲、或成形時引起所謂的過濾器阻塞等問題。 又，在使用來做爲觸媒的情況下，觸媒活性會顯著地下降 。比較好的含量範圍係0.1〜20;更宜是0.5〜10。 在本發明聚酯中鋁及其化合物之含量，以鋁原子計較理 想是0.5〜500 ppm。當銘原子之含量超過500 ppm時， 不僅會生成多量的起因於鋁原子之對聚酯不溶性異物，而 且會發生樹脂之熱安定性缺乏之問題，因而不佳。當鋁原 子含量少於0 . 5 ppm時，在使用來做爲觸媒的情況下，會 發生觸媒活性顯著下降，因而不宜。比較好的含量範圍係 在5〜70 ppm;更宜是在10〜40 ppm之範圍；特別好 的是在 15〜25 ppm之範圍。 24 1276646 五、發明說明（23) 在本發明之聚酯係爲一種因含有磷化合物而具有使鋁化 合物之觸媒活性提昇之效果，尙且能抑制異物之發生，並 經改善聚酯的熱安定性、及熱氧化安定性者。更且，藉由 含有苯酚系化合物，使得聚酯之熱氧化安定性更向上提高 一層，結果將可抑制聚酯之熱劣化及變黃。 再者，本發明之另一種聚酯.，其特徵在於：其係含有自 磷化合物所組成之群類中選出之至少一種，以及自苯酚系 化合物所組成之群類中選出之至少一種之聚酯；而且在該 聚酯中所含金屬原子之總量，相對於聚酯計係在1〇〇 ppm 以下。該聚酯係一種經改善成形時引起所謂的過濾器阻塞 之問題者，更且經改善熱安定性、及熱氧化安定性者。當 金屬原子之總量超過100 ppm時，聚酯中之異物會增加 而破壞聚酯之品質，因而不宜。當在聚酯中所含有的金屬 原子之總量在1 ppm以上時，在使用此種金屬來做爲觸 媒的情況下，可發揮觸媒活性，因而較佳。金屬原子之總 量較宜是 3〜50 ppm;更宜是5〜30 ppm。金屬種類並 沒有特別地限定，但較宜是自鹼金屬、鹼土金屬、與鋁中 選出一種以上者。 在本發明聚酯中磷及其化合物之含量，以磷原子計較理 想是1〜1000 ppm。當磷原子含量少於1 ppm時，不僅會 缺乏抑制生成對聚酯不溶性異物之效果，而且樹脂之熱安 定性會降低，因而不佳。當磷原子之含量超過1〇〇〇 ppm 時，會生成多量的起因於鋁原子之對聚酯不溶性異物，因 -25- 1276646 五、發明說明（24) 而不宜。比較好的含量範圍係在10〜200 ppm;更宜是在 20〜100 ppm之範圍。 又，另一方面，爲了使聚酯之熱安定性等物性增加，在 本發明之聚酯中較宜是含有自鹼金屬及其化合物、和鹼土 金屬及其化合物所組成之群類中選出之至少一種。依照減 低聚酯中之異物以及減低聚酯著色之觀點來看，彼等之中 較宜是含有自鋰、鈉、鉀、鎂、鈣及其化合物所組成之群 類中選出之至少一種。此等之中含有自鋰、鈣及其化合物 所組成之群類中選出之至少一種者，因會具有優良的聚酯 熱安定性而較佳。更且，依照減低聚酯著色之觀點來看， 較宜是含有自鈣及其化合物所組成之群類中選出之至少一 種者。 在本發明之聚酯中含有鹼金屬、鹼土金屬及其化合物之 情況下，其含量相對於構成聚酯的全部多元羧酸單位之莫 耳數計，宜是在從1 X 10·6以上到不足0·1莫耳％ ;較宜 是5 X 10·6〜0.05莫耳％ ;更宜是1 X 10·5〜〇·〇3莫耳 % ;特別合宜的是從1 X 1 (Γ5〜〇 · 〇 1莫耳％。由於鹼金屬 、鹼土金屬之含量爲少量時，將可減低熱安定性變差、耐 加氫分解性下降、發生異物、著色等問題。當鹼金屬、鹼 土金屬及其化合物之含量在0.1莫耳％以上時，將使得熱 安定性變差、發生異物及著色增加、耐加氫分解性下降等 製品加工上之問題。當其含量不足1 X 10·6莫耳％時，含 有之效果不明確。 -26- 1276646 五、發明說明（25) 本發明係關於一種使用上述之化合物做成之觸媒來製造 如上述這樣的聚酯之方法。 又，本發明之另一種聚酯必須是含有自鋁及其化合物所 組成之群類中選出之至少一種上，及自磷及其化合物所組 成之群類中選出之至少一種；而且聚酯中磷原子含量（ppm) 對鋁原子含量（ppm)之比値必須是在0.5 ~20之範圍。當 比値小於0.5時，會生成多量的對聚酯不溶性之異物，結 果在紡絲時頻繁地發生斷絲、或成形時引起所謂的過濾器 阻塞等問題。又，樹脂會顯著地著色，而破壞成形品外觀 等問題，也會發生樹脂之耐加氫分解性變差之問題。在該 比値超過20的情形下，會生成多量的對聚酯不溶性之異 物，結果在紡絲時頻繁地發生斷絲、或成形時引起所謂的 過濾器阻塞等問題。又，在使用來做爲觸媒的情況下，會 發生觸媒活性顯著下降的問題。比較好的範圍係1〜1 5 ; 更宜是3〜10〇 在本發明之聚酯中，由於係含有自鋁及其化合物所組成 之群類中選出之至少一種，以及自磷及其化合物所組成之 群類中選出之至少一種；且使其含量在上述範圍圍內，因 而具有抑制生成對聚酯不溶性的異物之效果，可改善在紡 絲時斷絲、或成形時過濾器阻塞等問題。 又，本發明之鋁及其化合物之含量，以在聚酯中之鋁原 子計較理想是1 ~ 100 ppm之範圍。當飽原子之含量超過 100 ppm時，不僅會生成多量的起因於鋁原子之對聚酯不 -27- 1276646 五、發明說明（26) 溶性異物，而且會發生樹脂之熱安定性缺乏之問題，因而 不佳。當鋁原子含量少於1 ppm時，在使用來做爲觸媒的 情況下，會發生觸媒活性顯著下降，因而不宜。比較好的 是係在5 ppm以上70 ppm以下之範圍；更宜是在1〇 ppm 以上30 ppm以下之範圍。 又，本發明磷化合物之含量，以在聚酯中之磷原子計較 理想是在5 ppm以上200 ppm以下之範圍。當磷原子含 量少於5 ppm時，會缺乏對生成聚酯不溶性異物之抑制效 果，又聚酯之熱安定性會變差，因而不佳。當磷原子之含 量超過200 ppm時，會生多量的聚酯不溶性之異物，因而 不宜。比較好的含量範圍係在10 ppm以上100 ppm以下 •，更宜是在20 ppm以上80 ppm以下。 在本發明之聚酯中磷化合物之存在態樣並沒有特別地限 定，但較宜是使用膦酸（phosphonic acid)系化合物、次 膦酸（phosphinic acid)系化合物、氧化膦（phosphine oxide)系化合物、亞膦酸（phosphonous acid)系化合物、 三價膦酸（phosphinous acid)系化合物、膦（phosphine) 系化合物中之任一形態。聚合聚酯時，使用具有此種構造 之磷化合物與鋁化合物共存者’會發現使觸媒活性增加之 效果。此等之中，當使用如膦酸系化合物態樣所做成之觸 媒時，會使得增加觸媒活性之效果變大，因而較佳。在膦 酸系化合物之中，爲使得增加觸媒活性之效果變大，較宜 是使用具有芳香環構造態樣者來做爲觸媒。 -28- 1276646 五、發明說明（27) 又，一方面，爲了使聚酯之熱安定性等物性增加，在本 發明之聚酯中較宜是含有自鹼金屬及其化合物、和鹼土金 屬及其化合物所組成之群類中選出之至少一種。依照減低 聚酯中之異物以及減低聚酯著色之觀點來看，彼等之中較 宜是含有自鋰、鈉、鉀、鎂、鈣及其化合物所組成之群類 中選出之至少一種。 在本發明之聚酯中含有鹼金屬、鹼土金屬及其化合物之 情況下，其含量相對於構成聚酯的全部多元羧酸單位之莫 耳數計，宜是在從1 X 10_6以上到不足0.1莫耳％ ;較宜 是5 X 10·6〜0.05莫耳％;更宜是1 X 10·5〜〇·〇3莫耳 % ;特別合宜的是從1 X 10·5〜0.01莫耳％。由於鹼金屬 、鹼土金屬之含量爲少量時，將可減低熱安定性變差、耐 加氫分解性下降、發生異物、著色等問題。當鹼金屬、鹼 土金屬及其化合物之含量在0 · 1莫耳％以上時，將使得熱 安定性變差、發生異物及著色增加、耐加氫分解性下降等 製品加工上之問題。當其含量不足1 X 1〇·6莫耳％時，含 有之效果不明確。 本發明係關於一種使用上述之金屬及化合物做成之觸媒 所製得之聚酯，及其製造方法。金屬及/或化合物之添加 量，必須是使在最終所得到的聚酯中之金屬原子及磷原子 含量如上述者。藉由該方法來改善對生成聚酯不溶性異物 之抑制效果，紡絲時斷絲、或成形時過濾器阻塞之問題。 本發明之聚酯，較宜不是使用銻化合物、鍺化合物、鈦 -29- 1276646 五、發明說明（28) 化合物、錫化合物等做成之聚合觸媒製造而得的。 又’ 一方面，本發明之聚酯，所使用的聚合觸媒係與銻 化合物、鍺化合物、鈦化合物、錫化合物等之聚合觸媒共 存使用之情況下，添加該等成分之添加量，較宜是在不會 產生如前述這種聚酯之特性、加工性、色調等製品上問題 、以縮短聚合時間並有效地提高生產性之範圍內。 本發明聚酯中銻原子之含量，當相對於聚酯計之量爲 50ppm以下時，將不會使聚酯變黑、並可抑制異物之發生 ，因而較佳。較宜是在30 ppm以下，更宜是在10 ppm 以下。另一方面，在本發明之聚酯中較宜是不含有銻原子 〇 又，本發明聚酯中鍺原子之含量，當相對於聚酯計之量 爲20 ppm以下時，將不會有成本上不利因素，因而較佳 。較宜是在10 ppm以下，更宜是在5 ppm以下。另一方 面，在本發明之聚酯中較宜是不含有鍺原子。 本發明聚酯中鈦原子之含量，當相對於聚酯計之量爲 5ppm以下時，聚酯之熱安定性及色調均優良，因而較佳 。較宜是在3ppm以下，更宜是在1 ppm以下。另一方面 ，本發明之聚酯較宜是不含有鈦原子。 更且，依照減低聚酯之著色觀點來看，本發明聚酯中’ 較宜是含有鈷及其化合物。但在聚酯中鈷及其化合物之含 量，宜是含有相對於聚酯計不足10 ppm之量。較宜是不 到5 ppm，更宜是在3 ppm以下。 -30- 1276646 五、發明說明（29) 已知鈷化合物係本身具有觸媒活性者，當添加程度使完 全發揮觸媒效果時，將會引起所得到的聚酯聚合物之透明 度下降、以及熱安定性變差。·在本發明中，藉由添加如上 述之少量鈷化合物以使得觸媒效果不明確這樣的添加量， 將具有消除得到的聚酯聚合物之透明度下降、以及消除熱 安定性變差、著色之效果。此外，在本發明中之鈷化合物 係具有消除著之目的，添加時期較宜是在聚合之階段，在 聚合反應終了後也沒有關係。 另一方面，爲了使聚酯聚合物之熱安定性及透明度變優 良，本發明之聚酯較宜是不含有鈷原子。 又，本發明之另一種聚酯聚合觸媒，其特徵在於：其系 由自鋁及其化合物所組成之群類中選出之至少一種，與自 磷化合物所組成之群類中選出之至少一種所構成，且磷原 子和鋁原子之比値係在0 · 5〜20之範圍。本發明之聚酯之 製造方法，其特徵在於：其係添加在上述範圍之自鋁及其 化合物所組成之群類中選出之至少一種，與自磷化合物所 組成之群類中選出之至少一種。當莫耳比小於〇.5時，則 觸媒活性會顯著下降，因而需要比聚合預定黏滯度之聚酯 更多的時間。莫耳比之較佳範圍係2〜1 5 ;更宜是3〜1 0 ; 特別合宜的是4〜8。 本發明中銘及其化合物之添加量，相對於構成聚酯的全 部多元羧酸單位之莫耳數，以鋁原子計較宜是〇〇〇1莫耳 %〜0.1莫耳％。當添加量超過0.1莫耳％時，將使得聚酯 -31 - 1276646 五、發明說明（3〇) 之熱安定性及熱氧化安定性變差、發生對聚酯不溶f生之胃 物及著色增加之問題。當其含量少於0 · 〇〇 1莫耳％時，貝U 無法充分地發揮觸媒之活性。比較佳的添加量範圍係 0.003莫耳％〜0.05莫耳％;更宜是0.005莫耳％〜〇〇2 吴耳％;特別合宜的是在0.007莫耳％〜0.015莫耳％。這 樣少量的鋁成分添加量之本發明聚合觸媒，係具有可顯示 充分的觸媒活性特點之巨大特徵。結果，將使得熱安定性 及熱氧化安定性變優良、並降低起因於鋁之異物、及著色 〇 本發明中磷化合物之添加量，相對於構成聚酯的全部多 元羧酸單位之莫耳數，以磷原子計較宜是0.005莫耳％ ~ 0.2莫耳％。當添加量少於0.005莫耳％時，則無法充分地 發揮添加效果。當添加量超過0 · 2莫耳％時，相反的在做 爲聚酯聚合觸媒之情況下，其觸媒活性會下降。比較佳的 添加量範圍係0.007莫耳％〜0.05莫耳％ ;更宜是〇.〇1莫 耳％〜0.02莫耳％。 不使用磷化合物而以鋁化合物爲主做爲觸媒成分之技術 ，雖然是一種可防止因減低銘化合物之使用量，並添加銘 化合物之以鋁化合物爲主觸媒成分，以致熱安定性降低而 著色的技術，但是當添加之程度是在鈷化合物具有充分之 觸媒活性下，則熱安定性會變差。從而，在技術上會有使 此兩者兼顧之困難。 設若依照本發明，則可藉由使用特定量的磷化合物，而 -3 2- 1276646 五、發明說明（31 ) 不會引起熱安定性降低、產生異物等問題，然而所得到的 是一種含金屬成分鋁之添加量係爲少量、但具有充分觸媒 效果的聚合觸媒；藉由使用此種聚合觸媒，將可改善聚酯 膜、瓶等中空成形品、纖維或工程塑膠等在熔融成形時之 熱安定性。在本發明磷化合物中，不宜是差不多看不到添 加磷酸、三甲基磷酸等磷酸酯之添加效果。又，在本發明 中所添加之本發明磷化合物之添加量範圍內，也可與含有 銻化合物、鈦化合物、錫化合物、鍺化合物等金屬之聚酯 聚合觸媒組合使用，但無法確認出促進熔融聚合反應之效 果。 又，本發明之其他的特徵係具有聚酯聚合觸媒，其特徵 在於：該觸媒係用於聚合具有熱安定性參數（TS)滿足下述 (9)式之聚對苯二甲酸乙二酯（PET); (9) TS < 0.20 ； (惟，TS爲將1克之特性黏滞度（[IVh )爲0.64〜 0.66 dl /克之PET放入試驗管中，以130°C真空乾燥12 小時之後，在非流通之氮氣氛圍氣下，在300°C維持熔融 2小時後，以下式來計算特性黏滯度（[IV] f )之數値）； TS = 〇·245 { [IV]，1.47 - [IVV1.47} 所謂的「非流通之氮氣氛圍氣」係指氮氣氛圍氣不流通 之意。例如，將樹脂薄片放入接續在真空管路上之試驗管 內，減壓並封入氮氣反復操作5次以上後，以1 00托利封 入氮氣使成爲封管狀態。 -33- 1276646 五、發明說明（32) 藉由使用此種構成之觸媒，乃可得到相對於一種薄膜、 瓶、纖維等之成形品等製造時.，賦予加熱熔融之熔融熱安 定性爲顯著優良，發生分子量降低、著色或異物少的成形 品。 TS較宜是在0 . 1 7以下，特別好的是在0 · 1 5以下。 向來，並不知道··能賦予TS在上述範圍之PET的聚酯 聚合觸媒。依照本發明不但發現能賦予TS在上述範圍之 PET的聚酯聚合觸媒；而且本發明之另一特徵係在於發現 :由使用該種聚酯聚合觸媒之聚合聚酯以形成的薄膜、瓶 等之中空成形品、纖維工程塑膠等，在進行熔融成形之際 可明顯地改善其熱安定性，而且即使是使用黏合之樹脂、 或再利用成形時所發生的碎屑亦可得到品質優良的製品。 用來做爲觸媒構成成分者，較宜是自上述聚酯聚合觸媒 爲磷成分所組成群類中選出之至少一種。 另一種本發明之聚酯聚合觸媒，係爲金屬或金屬化合物 與磷化合物所形成之物，其特徵在於：活性參數（AP)滿足 下述（10)式； (10) AP (分）< APX (分）； (惟，AP係代表使用預定量之觸媒，在27 5°C、0.1托利 之減壓度下，聚合特性黏滯度爲0.65 dl /克之聚對苯 二甲酸乙二酯（PET)所需要的時間（分）；APX係代表只有上 述金屬或金屬化合物時，在與上述同樣的用量、同樣的條 件下聚合PET所需要的時間（分））。 -34- 1276646 五、發明說明（33) AP之測定方法，具體而言係如以下所述。 1) (BHET製造步驟）使用2倍於對酞酸莫耳量的乙二 醇，以製造酯化率爲95%之雙（2-羥乙基）對酞酸酯（MET) 及寡聚物之混合物（以下，稱爲BHET混合物）。 2) (觸媒添加步驟）添加預定量之觸媒到上述BHET混 合物中，於氮氣氛圍氣，常壓、245°C下攪拌10分鐘，接 著以50分鐘昇溫至275°C爲止，繼續將寡聚省混合物之反 應壓力慢慢地下壓降至〇 . 1托利。 3) (聚縮合步驟）於275 °C、0.1托利下進行聚縮合反 應，使聚合直到聚對苯二甲酸乙二酯之特性黏度（IV)達到 0.65 dl/克爲止。 4) 在聚縮合步驟中所需要的聚合時間即爲AP(分鐘）。 在此，係使用批式反應裝置來進行。 1 )( BHET製造步驟）BHET混合物之製造，係可以使用 公知的方法來進行。例如，將2倍於對酞酸莫耳量的乙二 醇投入附有攪拌機之批式高壓釜中，以0.25 MPa加壓、 於245°C下餾去系統外之水分，接著藉由進行酯化反應製 造。 藉使活性參數AP在上述範圍內，不僅使熱安定性因磷 化合物之共存而提高，而且反應速度變得比較快速，因而 聚聚縮合聚酯之製造時間會更短縮。AP較宜是在0 . 9 APX 以下，更宜是在0.8 APX以下，特別良好的是在0.7 APX 以下。 -35- 1276646 五、發明說明（34) 2 )(觸媒添加步驟）中「預定量之觸媒」係指因應觸媒 活性而變更觸媒使用量之意；活性高之觸媒使用量少，活 性低之觸媒用量較多。 一般來說，磷化合物已知係用來做爲聚酯之安定劑，雖 然已知可抑制聚酯之熱劣化；.但是向來並不知道：活性參 數AP係在上述範圍內之由金屬、或金屬化合物、與磷化 合物所成的聚酯聚合觸媒。實際上，以聚酯聚合觸媒之代 表性觸媒，即銻化合物、鈦化合物、或鍺化合物做成之聚 合觸媒來聚合物聚酯之際，添加磷化合物係無法確認出具 有促進聚合之實質上的作用。依照本發明係發現一種活性 參數AP係在上述範圍內之由金屬、或金屬化合物、與磷 化合物所成的聚酯聚合觸媒，其特徵在於：由於使用該種 聚酯聚合觸媒，其觸媒活性優良，在觸媒之失活或沒有除 去時，能賦予抑制在熔融成形時的熱劣化效果，而得到熱 安定性優良的聚酯之聚合觸媒。 上述之聚酯聚合觸媒，較宜是進一步使用該觸媒所聚合 聚對苯二甲酸乙二酯（PET)之熱安定性參數（TS)乃滿足下 述（9)式： (9) TS < 0.20 藉由使用此種構成之觸媒，其觸媒活性優良，而且可得 到一種對於薄膜、瓶、纖維等成形品製造時之加熱熔融， 其熔融熱安定性係爲明顯的良好，並賦予產生分子量降低 、著色、異物少的成形品之聚酯。 -36- 1276646 五、發明說明（35) TS較宜是在〇 · 1 8以下；特別良好的是在0 · 1 5以下。 本發明之聚酯聚合觸媒，較宜是使用該觸媒所聚合聚對 苯二甲酸乙二酯（PET)之熱氧化安定性參數（TOS )乃滿足下 述（11 )式： (11) TOS < 0.10 上述式中，TOS係指將經熔融聚合之 IV爲 0.64〜0.66 dl/克之PET樹脂片，予以冷凍粉碎成20篩 目以下之粉末，取0.3克之經在130°C真空乾燥12小時者 放入試驗管中，以70°C真空乾燥12小時之後，在以矽膠 乾燥之空氣下，以 230°C加熱15分鐘後，利用下式來計 算其I V値； TOS = 0·245 { [IV]fi·147 - [IV]，1.47} [IV] i及[IV]fl分別爲加熱試驗前和加熱試驗後之 IV(dl/克））。 以藉矽膠乾燥空氣之加熱方法的例子，例如是以充塡矽 膠之乾燥管接續於玻璃試驗管上端，以乾燥之空氣加熱方 法。 藉由使用上述構成之觸媒，可得到一種能賦予優良耐熱 老化性之薄膜，以及如瓶之成形品。 TOS較宜是在0.09以下；特別良好的是在0.08以下。 在本發明中測定TS、TOS所使用的PET樹脂薄片，其係 使用經上述1)〜3)之步驟後，再藉由從熔融狀態急冷而製 得之物。在此所所用的樹脂薄片的形狀，例如是使用長度 -37- 1276646 五、發明說明（36) 約爲3毫米、直徑約爲2毫米之圓柱形狀的樹脂薄片。 又，本發明之聚酯聚合觸媒.，其活性參數（AP)較宜是滿 足下式（1 2 ): (12) AP (分）< 2T (分） T係代表相對於以三氧化銻做爲觸媒所生成的聚對苯二 甲酸乙二酯中之酸成分計，使銻原子爲0.05莫耳％這樣添 加情況下之AP。 在本發明中爲比較而用的三氧化銻，使用純度在99%以 上之三氧化銻。例如，使用市售的銻（ΙΠ )氧化物（阿迪里 奇化學公司製，純度爲99.99 9%)。 爲了使以聚縮合來製造聚酯之時間縮短，較宜是藉由使 活性參數AP在上述範圍內，以加快反應速度。AP較宜是 在1 . 5T以下，更宜是在1 . 3T以下，特別良好的是在1 .0T 以下。 可做爲構成本發明之聚酯聚合觸媒的金屬成分者，舉例 來說，除了銻、鈦、鍺以外並沒有特別地限定爲某種物質 ，但較宜是如鹼金屬、鹼土金屬、鋁或鎵等DIA族元素； 矽等之IV族元素；各種過渡金屬；以及鑭系元素等等。在 彼等之中，以IE A族元素較理想，其中又較宜是鋁。該金 屬之化合物，舉例來說，雖然並沒有特別地限定，但具體 來說較宜是該金屬之甲酸、乙酸、丙酸、丁酸、草酸等之 飽和脂肪族羧酸；丙烯酸、甲丙烯酸等之不飽和脂肪族羧 酸；安息香酸等之芳香族羧酸鹽；三氯乙酸等之含鹵素羧 -38- 1276646 五、發明說明（37) 酸鹽；乳酸、檸檬酸、柳酸等之羥基羧酸鹽；碳酸、硫酸 、硝酸、磷酸、膦酸、碳酸氫、磷酸氫、硫化氫、亞硫酸 、硫代硫酸、鹽酸、溴化氫酸、氯酸、溴酸等之無機酸鹽 ;1-丙烷磺酸、1-戊烷磺酸、.萘磺酸等之有機磺酸；月桂 基硫酸等之有機硫酸鹽；甲氧、乙氧、丙氧、異-丙氧 、η -丁氧、第三-丁氧等之烷氧化物；乙醯乙酸酯等之螫 合化合物；氫化物、氧化物、氫氧化物等。 製造聚酯時上述金屬成分之較佳使用量’雖然係隨使用 的金屬種類而不同；但相對於構成聚酯所有的多羧酸單位 之莫耳數計，較宜是在在從1 X 1〇·6以上0.5莫耳％以下 ;更宜是5 X 10·5〜0.1莫耳％。當添加量係超過0.5莫 耳％時，因所得到的聚酯之熱安定性及色調等品質會降低 而不宜。當添加量係爲不滿1 X W6莫耳％時，則因添加 之效果不明確而不宜。 本發明之聚酯聚合觸媒，較宜是含有自鋁及其化合物所 組成之群類中選出之至少一種來做爲觸媒之構成成分者。 本發明中不是鋁的鋁化合物之使用量，相對於聚酯中二 羧酸及多元羧酸等之羧酸成分全部構成單位之莫耳數計， 較宜是在從0.001〜0.05莫耳％;更宜是0.005〜0.02 莫耳％。當使用量係爲不滿0.001莫耳％的情形下，則觸媒 之活性將不能充分地發揮；當使用量係超過0.0 5莫耳％時 ，因熱安定性及熱氧化安定性之降低，則會產生起因於鋁 之異物以致著色增加之問題。具有這樣少量之鋁成分添加 -39- 1276646 五、發明說明（38) 量，也是本發明聚合觸媒顯示充分的觸媒活性特點之重大 特徵。由此結果所得到的熱安定性及熱氧化安定性均優， 並使起因於鋁之異物及著色降低。 本發明中磷化合物之使用量，相對於聚酯中多羧酸成分 之全部構成單位的莫耳數計，較宜是在從0.0001〜〇. 1 莫耳％ ;更宜是0.005〜0.05莫耳％。當磷化合物之添加 量係爲不滿0.0001莫耳％時，則因添加之效果不明確；當 磷化合物之添加量係超過0 . 1莫耳％時，相反的做爲聚酯 之觸媒活性會下降。 不使用磷化合物而以鋁化合物爲主的觸媒成分之技術， 是一種減低鋁化合物之使用量，進而在添加鈷化合物之以 鋁化合物爲主觸媒的場合下，藉由熱安定性之降低而防止 著色之技術，但是添加鈷化合物到具有充分觸媒活性之程 度時，還是會使熱安定性下降。從而，此種技術係有兩者 兼顧之困難。 設若依照本發明，將可藉由使用特定量的磷化合物，而 不會引起熱安定性降低、產生異物等問題，然而可得到一 種含金屬成分中鋁之添加量係爲少量、但具有充分觸媒效 果的聚合觸媒；藉由使用此種聚合觸媒，將可改善聚酯膜 、瓶等中空成形品、纖維或工程塑膠等在熔融成形時之熱 安定性。在本發明磷化合物中，不宜是差不多看不到添加 磷酸、三甲基磷酸等磷酸酯使觸媒活性提昇之添加效果。 又，在本發明中所添加之本發明磷化合物之添加量範圍內 -40- 1276646 五、發明說明（39 ) ，也可與含有銻化合物、鈦化合物、鍺化合物等化合物組 合來使用，但無法確認出促進熔融聚合反應之效果。 做爲本發明之聚酯聚合觸媒的構成成分，較宜是含有自 磷化合物之鋁鹽中選出之至少一種。與磷化合物之紹鹽以 外的鋁化合物、或磷化合物等組合來使用也可以。 本發明中磷化合物之鋁鹽的使用量，相對於聚酯中多羧 酸成分之全部構成單位的莫耳數計，較宜是在從0.0001〜 0_2莫耳％;更宜是0.005〜0.1莫耳％。 又，本發明之另外的特徵，其係以預先溶解在水及/或 有機溶劑中之羧酸鋁鹽來做爲觸媒使用。 做爲本發明之羧酸鋁鹽者，舉例來說，具體而言係如甲 酸鋁、乙酸鋁、鹼基乙酸鋁、丙酸鋁、草酸鋁、丙烯酸鋁 、月桂酸鋁、硬脂酸鋁、苯甲酸鋁、三氯乙酸鋁、乳酸鋁 、枯酸鋁、酒石酸鋁、柳酸鋁等；但是依照溶解性、及觸 媒媒活性之觀點來看，較宜是具有乙酸鋁、鹼基乙酸鋁等 之醋酸鋁鹽構造之物、或乳酸鋁系。 使用羧酸之鋁鹽來做爲聚酯聚合觸媒之例子，舉例來說 ，例如是乙酸鋁、鹼基乙酸鋁、乳酸鋁、苯甲酸鋁等，但 是由於其中之任一者對聚酯之溶解性低，同時觸媒活性也 差，因而將會有生成對所得到的聚酯不溶性之異物的問題 ，而且使用此等化合物來做爲觸媒照樣會有問題。依照本 發明，使用預先溶解在水及/或有機溶劑中之物來做爲觸 媒，將可發現持有充分的觸媒活性特點之重大特徵。 -41 - 1276646 五、發明說明（4〇) 本發明之羧酸鋁鹽係必須在添加到聚酯的聚合系之前， 預先使成爲溶解在水及/或有機溶劑中之狀態，然後再添 加到聚合系。用來做爲有機溶媒者，較宜是二醇類；於製 造PET之情況下較宜是使用乙二醇。 可當做具有乙酸之鋁鹽之構造物者，舉例來說，例如是 鹼基乙酸鋁、三乙酸鋁、乙酸鋁溶液等；其中，依照溶解 性及溶液之安定性觀點來看，較宜是使用鹼基乙酸鋁。將 任一者之鹼基乙酸鋁予以溶解在水及/或有機溶劑中以做 爲觸媒來使用是有必要的。藉由使用此種構成的觸媒，將 可以得到觸媒活性優良、品質優異的聚酯。做爲溶劑者， 較宜是使用水或二醇類來；在製造PET的情況下，較宜是 使用水或乙二醇。 又’依照本發明，當使用經硼酸等安定化之羧酸鋁鹽來 做爲觸媒時，將可發現得到一種溶解性及溶液之安定性均 爲優良，同時觸媒活性也優異，品質優良的聚酯之重大特 徵。可當做羧酸之鋁鹽，較宜是具有乙酸之鋁鹽之構造者 ;其中較宜是使用鹼基乙酸鋁。可做爲安定劑者，除了硼 酸以外舉例來說係有尿素、硫基脲等，但較宜是使用硼酸 。在使用硼酸安定化之情況下，較宜是使用莫耳量二在鋁 量以下之硼酸予以安定化者，此時較宜是使用以1 / 2〜 1 / 3莫耳量之硼酸使安定化之鋁化合物。從觸媒活性及聚 酯之品質觀點來看，較宜是添加預先溶解在水及/或有機 溶劑中之經溶解的聚合系。做爲有機溶媒者，較宜是使用 -42- 1276646 五、 發明說明（41 ) 二 醇類 來 ;在製造 PET的情況下，較宜是使用乙二醇。 在W0 98/42769 中，係揭示一種以預先將鹼基乙酸鋁 與 氫 氧化 四 乙胺等之 鹼性化合物予以混合之物來做爲觸媒 使 用 。該 方 法雖然記 載著一種抑制不溶性異物之形成的方 法 但是 依 照該技術 則必須使用鹼性化合物；因而會有生成 起 因於 鹼 性化合物 使聚酯著色或異物之問題。依照本發 明 則該 專 利所記載 的鹼性化合物與本發明之鋁化合物並不 需 要預 先 混合，所以可得到降低上述著色及異物問題之 聚 酯 〇 爲了 製 造本發明 之預先將羧酸鋁予以溶解在水及/或 有 機 溶劑 中 之溶液， 較宜是使用將羧酸鋁予以溶解在水中 之 溶 液。 該 水溶液中 ，較宜是視情況地加入二醇類等之有 機 溶 劑。 將 該水溶液 添加在原來的聚合系中也可以，爲了 減 熱 衝擊 較宜是添 加用乙二醇等二醇類將該溶液稀釋之 物 到 聚合 系 中，或者 添加以二醇類予以稀釋之溶液經液- 液 取代及 餾 除水分之 物到聚合系中。 在用 乙 二醇等二 醇類將該溶液予以稀釋之情況下，較 宜 是 以相 對 於水之容 量比計爲0.5〜50倍量之二醇類來稀 釋 之 。又 爲使難以 生成在所得到的聚酯中之不溶性異物 並 抑 制之 巨 的，添加 至聚合系中之羧酸鋁溶液之濃度，較 宜 是 換算 成 鋁原子計 爲0.01〜1莫耳/升。 在將 :羧酸鋁鹽彳 容解於水及/或有機溶劑中之時、 或 在 已溶解之溶液 中添加硼酸等‘之安定劑、或檸檬 酸 -43- 1276646 五、發明說明（42)、乳酸、草酸等之酸，由於於可提高溶解性及溶液 之安定性，因而較理想。 以下所例示者，係爲在將本發明所使用的鹼基乙酸鋁溶 解在水及/或有機溶劑中而調製成溶液之方法的具體例。 <鹼基乙酸鋁之水溶液的調製例> 將鹼基乙酸鋁加入水中於室溫下攪拌數小時以上。攪拌 時間較宜是12小時以上。之後，在60°C以上進行攪拌數 小時。此種場合下之溫度，較宜是在60〜80 °C之範圍 。攪拌時間較宜是在3小時以上。水溶液之濃度較宜是5 克/升〜100克/升；更宜是在10克/升〜30克/升。 <鹼基乙酸鋁之乙二醇溶液的調製例> 將相對的乙二醇加入上述水溶液。乙二醇之添加量，相 對於水溶液之容量比計，較宜是1〜5倍量。更宜是2〜 3倍量。在常溫下將該溶液予以攪拌數小時，以得到均一 的水/乙二醇混合溶液。之後，加熱該溶液，餾除水而得 到乙二醇溶液。溫度較宜是在80°C以上，120°C以下。更 宜是在90〜110 °C攪拌數小時以餾除水分。 以下所例示者，係爲在將本發明中所使用的乳酸鋁之乙 二醇溶液之調製方法的具體例。 調製乳酸鋁之水溶液。調製係可以在室溫或加熱下進行 ，較宜是在室溫下。水溶液之濃度較宜是20克/升~ i 00 克/升；更宜是在50克/升〜80克/升。將乙二醇添加到 該水溶液中。乙二醇之添加量，相對於水溶液之容量比計 -44- 1276646 五、發明說明（43) ，較宜是1〜5倍量。更宜是2〜3倍量。在常溫下將該 溶液予以攪拌而得到均一的水/乙二醇混合溶液之後，加 熱該溶液，餾除水而得到乙二醇溶液。溫度較宜是在80°C 以上，120°C以下。更宜是在90〜110 °C攬拌數小時以 餾除水分。 將具有本發明聚酯聚合觸媒之羧酸鋁鹽予以溶解在水及 /或有機溶劑所成之溶液中，較宜是添加自磷化合物所組 成之群類中選出之至少一種，以使得溶液之安定性增加， 並抑制異物之形成。在將羧酸鋁鹽予以溶解在水及/或有 機溶劑以調製溶液之時，也可以和磷化合物所組成之群類 中選出之至少一種共存。磷化合物之添加量，相對於鋁原 子計之磷原子的莫耳比，較宜是在0.1〜10之範圍。磷化 合物之添加方法，將磷化合物添加在預先調製的鋁化合物 溶液中也可以，將鋁化合物予以溶解在預先調製的磷化合 物溶液中也可以。或者，將兩種溶液予以混合來調製也可 以，將兩者同時溶解在溶劑中也可以。做爲溶劑者，較宜 是使用水或二醇類來；在製造PET的情況下，較宜是使用 水及/或乙二醇。 根據本發明之方法來製造聚酯時，相對於聚酯中二羧酸 及多元羧酸等之羧酸成分的全部構成單位之莫耳數計，鋁 原子宜是0.01〜0.05莫耳％，更宜是0.005〜0.02莫 耳％。當使用量係不滿0 · 00 1莫耳％時，則觸媒活性係難以 充分地發揮；當使用量係在〇.〇5莫耳％以上時，熱安定性 -45- 1276646 五、發明說明（44 ) 或熱氧化安定性會降低，而發生起因於鋁化合物之對聚酯 不溶性之異物、或著色增加之問題。具有這樣少量之鋁成 分添加量，也是本發明聚合觸媒顯示充分的觸媒活性特點 之重大特徵。由此結果所得到的熱安定性及熱氧化安定性 均優，並使起因於鋁之異物及著色降低。 根據本發明之方法，在製造聚酯之際，當使用自磷化合 物所組成之群類中選出之至少一種時，將可發現具有改善 聚合物之熱安定性等物性之效果。 根據本發明之方法，在製造聚酯之際所使用的磷化合物 之量，相對於聚酯中多元羧酸之全部構成單位之莫耳數計 ，鋁原子宜是0.0001〜0. 1莫耳％，更宜是 0.005〜 0.05莫耳％。在使用具有本發明聚酯聚合觸媒之羧酸鋁鹽 中添加磷化合物所做成之觸媒的情況下，該觸媒之添加量 較宜是將磷化合物之添加量調節在上述之範圍內。在添加 磷化合物之觸媒溶液以外的場合下，在聚合系中所添加的 磷化合物之總量較宜是在上述之範圍內。 藉由倂用之本發明的磷化合物，將可使得在聚酯聚合觸 媒中，以少量添加之鋁而得到充分發揮觸媒效果之觸媒。 磷化合物之添加量係不滿〇 · 〇〇〇 1莫耳％時，則難以充分地 發揮添加觸媒之效果；又，，當添加量係超過〇 . 1莫耳％ 時，則相反的會成爲觸媒活性降低之情況，該降低之傾向 係視鋁之使用量等而變化。 根據本發明之方法來製造聚酯之場合下，較宜是不添加 -46 - 1276646 五、發明說明（45) 鹼金屬、鹼土金屬或其化合物。 又，一方面，在本發明中較佳的具體實施例，係爲添加 含有在鋁及其化合物中加入少量的自鹼金屬、鹼土金屬及 其化合物所組成之群類中選出之至少一種之第2金屬成分 。又，本發明之聚酯聚合觸媒之具體實施例，較宜是與上 述第2金屬含有成分共存。又，於聚合時，在本發明之聚 酯聚合觸媒的溶液中，添加含有自鹼金屬、鹼土金屬及其 化合物所組成之群類中選出之至少一種者也可以，添加自 鹼金屬、鹼土金屬及其化合物所組成之群類中選出之至少 一種到其他的觸媒溶液中也可以。添加此種第2金屬含有 成分時，除了具有抑制二乙二醇之生成效果之外，尙可得 到高觸媒活性；從而可得到比較高反應速度之觸媒成分， 而使得生產性有效地提高。 在鋁化合物中添加鹼金屬化合物或鹼土金屬化合物，以 得到具有充活性之觸媒，係爲一種公知的技術。使用此種 公知的觸媒時，雖然可得到熱安定性優良的聚酯，但是與 鹼金屬化合物、鹼土金屬化合物倂用的公知觸媒，則有必 要是添加多於得到實用的觸媒活性之量，則起因於使用鹼 金屬之異物量會變多；在纖維上使用的製絲性或絲物性、 或者在薄膜上使用時之薄膜物性、透明性、熱安定性、熱 氧化安定性、耐加氫分解性等均會惡化。更且，纖維或薄 膜等之熔融成形品之色調亦會惡化。又，在與鹼土金屬化 合物倂用的場合下，爲得到實用的活性，則所得到的聚酯 -47- I276646 五、發明說明（46) &熱安定性、熱氧化安定性均會降低，因加熱而著色會變 大，異物之產生量也會變多。 在添加鹼金屬、鹼土金屬及其化合物之場合下，其使用 釐Μ (莫耳％ )，其含量相對於構成聚酯的全部多元竣酸單位 之莫耳數計，宜是在從1 X 1 0 ·6以上到不足0 · 1莫耳％ ; 較宜是5xl〇·6〜0.05莫耳％;更宜是1 ΧΙΟ.5〜〇.〇3 莫耳％ ;特別合宜的是從1 X 10·5 ~ 0.01莫耳％。由於鹼 金屬、鹼土金屬之含量爲少量時，將可減低熱安定性變差 、耐加氫分解性下降、發生異物、著色等問題。當鹼金屬 、鹼土金屬及其化合物之使用量Μ係在0.1莫耳％以上時 ’將使得熱安定性變差、發生異物及著色增加、耐加氫分 解性下降等製品加工上之問題。當Μ係爲不足1 X 1 〇·6莫 耳％時，含有之效果不明確。 根據本發明之方法來製造聚酯之際，其較佳之具體實施 例，係爲進一步添加相對於聚酯計，鈷原子爲不滿10 ppm 之銘化合物。較宜是在5 ppm以下，更宜是在3 ppm修以 下。又，在聚合時預先於本發明之聚酯聚合觸媒中，添加 含有鈷化合物之物也可以；在觸媒溶液之外另外添加鈷化 合物也可以。 又，一方面，根據本發明之方法來製造聚酯之際，較宜 是不使用鈷化合物。 根據本發明之方法來製造聚酯之際，添加如銻化合物、 鈦化合物、鍺化合物、錫化合物等其他的聚合觸媒之成分 -48- 1276646 五、發明說明（47) ，其共存使用之添加量較宜是落在不會生成前述那樣在聚 酯特性、加工性、色調等製品上問題之範圍內，並有利於 縮短聚合時間、提高生產性。 但是，銻化合物之可添加量，相對於聚合所得的聚酯計 ，其銻原子之含量宜是在50 ppm以下，更宜之添加量是 在30 ppm以下。當鍊之添加含量比50 ppm多時，會引 起金屬銻之析出，而使聚酯變黑並發生異物，故不宜。 鈦化合物之可添加量，相對於聚合所得的聚酯計，其鈦 原子之含量宜是在10 ppm以下之範圍。較宜是在5 ppm 以下，更宜是在2 ppm以下。當鈦之添加含量比10 ppm 多時，所得到的樹酯之熱安定性會顯著地下降。 鍺化合物之可添加量，相對於聚合所得側的聚酯計，其 銻原子之含量宜是在20 ppm.以下，更宜之添加量是在 10 ppm以下。當鍺之添加量比20 ppm多時，因不利於 成本，故不宜。 根據本發明之方法來製造聚酯之際，係可以使用銻化合 物、鈦化合物、鍺化合物、錫化合物中之1種或者是2種 以上。 可做爲本發明之鹼金屬及其化合物、和鹼土金屬及其化 合物者，並沒有特別地限定爲某種物質，舉例來說，例如 是該金屬之甲酸、乙酸、丙酸.、丁酸、草酸等之飽和脂肪 族羧酸；丙烯酸、甲丙烯酸等之不飽和脂肪族羧酸；安息 香酸等之芳香族羧酸鹽；三氯乙酸等之含鹵素羧酸鹽；乳 -49- 1276646 五、發明說明（48) 酸、檸檬酸、柳酸等之羥基羧酸鹽；碳酸、磷酸、硝酸、 硫酸、膦酸、碳酸氫、磷酸氫、硫化氫、亞硫酸、硫代硫 酸、鹽酸、溴化氫酸、氯酸、溴酸等之無機酸鹽；1-丙烷 磺酸、1-戊烷磺酸、萘磺酸等之有機磺酸；月桂基硫酸等 之有機硫酸鹽；甲氧、乙氧、η-丙氧、異-丙氧、n-丁氧 、第三-丁氧等之烷氧化物；乙醯乙酸酯等之螫合化合物 ;氫化物、氧化物、氫氧化物等。 此等化合物中，當使用氫氧化物等強鹼性物之情形下， 因爲具有難以溶解在乙二醇等之二醇或乙醇等之有機溶媒 中之傾向，因而具有不得不以水溶液添加到聚合系之聚合 程序上之問題。更且，在使用氫氧化物等強鹼性物之情形 下，在聚合時之聚酯容易受到加氫分解等之副反應，使得 聚合之聚酯具有易於著色之傾向，以致耐加氫分解性具有 降低之傾向。從而，較適合來做爲本發明之鹼金屬及其化 合物、和鹼土金屬及其化合物者，例如是該金屬之飽和脂 肪族羧酸；不飽和脂肪族羧酸、芳香族羧酸鹽、含鹵素羧 酸鹽、羥基羧酸鹽、硫酸、硝酸、磷酸、膦酸、磷酸氫、 硫化氫、亞硫酸、硫代硫酸、鹽酸、溴化氫酸、氯酸、溴 酸等中所選出之無機酸鹽；有機膦酸鹽、有機硫酸鹽、螫 合化合物、氧化物等。更且，此等之中，依照取得容易、 入手容易等之觀點來看，較宜是有機羧酸鹽，特別是使用 乙酸鹽。 可做爲本發明之鋁及其化合物者，並沒有特別地限定爲 -50- 1276646 五、發明說明（49) 某種物質，但除了金屬鋁以外，舉例來說，例如也可以使 用甲酸鋁、乙酸鋁、鹼基乙酸鋁、丙酸鋁、草酸鋁、丙烯 酸鋁、月桂酸鋁、硬脂酸鋁、安息香酸鋁、三氯乙酸鋁、 乳酸鋁、酒石酸鋁、檸檬酸鋁、柳酸鋁等之羧酸鹽；氯化 鋁、氫氧化鋁、氫氧化氯化鋁、多元氯化鋁、硝酸鋁、磷 酸鋁、碳酸鋁、磷酸鋁、膦酸鋁等之無機酸鹽；鋁甲氧化 物、鋁乙氧化物、鋁η-丙氧化物、鋁異丙氧化物、鋁η-丁氧化物、鋁t - 丁氧化物等之鋁烷氧化物；鋁乙醯丙酮、 鋁乙基乙醯乙酸鹽、鋁乙基乙醯丙酮、鋁乙基乙醯乙酸鹽 二異-丙氧化物等之鋁螫合化物；三甲基鋁、三乙基鋁等 之有機鋁化物或其部分加氫分解物；由鋁之烷氧化物或鋁 螫合化物與羥基羧酸而來之反應生成物；氧化鋁、超微粒 子氧化鋁、矽酸鋁、鋁和鈦或矽或銷或鹼金屬或鹼土金屬 等之複合氧化物等。在彼等之中，理想上使用羧酸鹽、無 機酸鹽及螫合化合物；更且其最好是鹼基醋酸鋁、氯化鋁 、氫氧化鋁、氫氧化氯化鋁、及鋁乙酸乙醯鹽。更宜是使 用經鹼基乙酸鋁等之添加劑予以安定化之物。 可做爲本發明之磷化合物者，雖然並沒有特別地限定， 但舉例來說，例如是如三甲基磷酸、三乙基磷酸、苯基磷 酸、三苯基磷酸等之磷酸的磷酸酯；如三甲基亞磷酸酯、 三乙基亞磷酸酯、三苯基亞磷酸酯、三（2, 4 -二-第三-丁 基苯）亞磷酸酯、四（2,4-二-第三-丁基苯）4,4'-二伸苯 基二亞磷酸酯等之亞磷酸的亞磷酸酯。 -51 - 1276646 五、發明說明（5〇) 本發明之比較好的磷化合物，較宜是自膦酸系化合物、 次膦酸系化合物、氧化膦系化合物、亞膦酸系化合物、三 價膦酸系化合物、膦系化合物組成群類中所選出之至少一 種磷化合物。藉由含有此種磷化合物來提高改良本發明目 標聚酯之物性效果，尙且在聚合聚酯中共存使用此種磷化 合物與本發明之鋁化合物時，可發現使觸媒活性增加之效 果。此等之中，當使用膦酸系化合物時，會使得增加觸媒 活性之效果變大，因而較佳。在上述磷化合物中，當使用 具有芳香環構造之化合物時，改善物性與觸媒活性之效果 會變大，因而較適宜。當製造本發明之聚酯時，藉由使用 此種的磷化合物，以得到一種使得鹼金屬化合物或鹼土金 屬化合物之添加量變爲少量，且充分發揮觸媒效果之觸媒 〇 就本發明來說，所謂的膦酸系化合物、次膦酸系化合物 、氧化膦系化合物、亞膦酸系化合物、三價膦酸系化合物 、膦系化合物，係指具有以下述各式（（化1)〜（化6))所 代表之構造的化合物而言。 -52- 1276646 五、發明說明（51) i<tn 〇 t II II 一〇一P—〇一 .I [化2] 〇 II II 一 P — 〇“ I I [化.3] 〇 II II 一F — I [:化 4] —〇一P —〇一 I , [化5] —P — 〇一 I [化6] 一 P-I -53- 1276646 五、發明說明（52) 可做爲本發明之膦酸系化合物者，舉例來說，例如是甲 基膦酸二甲酯、甲基膦酸二苯酯、苯基膦酸二甲酯、苯基 膦酸二乙酯、苯基膦酸二苯酯、苄基膦酸二甲酯、苄基膦 酸二乙酯等。可做爲本發明之次膦酸系化合物者，舉例來 說，例如是二苯基次膦酸、二苯基次膦酸甲酯、二苯基次 膦酸苯酯、苯基次膦酸、苯基次膦酸甲酯、苯基次膦酸苯 酯等。可做爲本發明之氧化膦系化合物者，舉例來說，例 如是二苯基膦氧化物、甲基二苯基膦氧化物、三苯基膦氧 化物等。 在次膦酸系化合物、氧化膦系化合物、亞膦酸系化合物 、三價膦酸系化合物、膦系化合物中，本發明之磷化合物 較宜是以下述各式（（化7)〜（化12))所代表之化合物。 [化7]〇4η OH [化8]1276646 V. INSTRUCTION DESCRIPTION (1) * [Technical Field] The present invention relates to a method for producing a polyester polymerization catalyst, a polyester and a polyester; and more particularly, the present invention relates to an filtration which can be used to improve molding. A polyester polymerization catalyst, a polyester, and a method for producing the same. [Background Art] Polyester, particularly polyethylene terephthalate (hereinafter abbreviated as PET), which has excellent mechanical properties and chemical properties and is used in various applications, for example, in clothing and industrial materials. For the use of various films or sheets, bottles and engineering plastics, such as fibers, packaging and magnetic tapes, PET is industrially based on citric acid or dimethyl phthalate, and ethylene glycol. Esterification or transesterification to produce bis(2-hydroxyethyl)-p-phthalate, which is obtained by condensation polymerization at high temperature under vacuum using a catalyst. As the catalyst used in the polycondensation, antimony trioxide is widely used. Although antimony trioxide is a catalyst which is inexpensive and excellent in catalytic activity, it is caused by precipitation of metal ruthenium during polycondensation, which not only causes blackening of PET but also causes problems such as foreign matter. Throughout this, it is often desirable to have a polyester that is completely free of bismuth or that does not contain ruthenium as a main component of the catalyst. Further, the foreign matter in the above-mentioned polyester causes problems such as, for example, (1) in the case of the polyester for a film, the metal ruthenium will become a foreign matter in the polyester, and will become a contamination when it is melted and extruded. The reason for the mold 'is also the cause of the surface defects of the film. Further, in the case of a raw material such as a hollow product, such as a hollow product, it is difficult to obtain a hollow molded article having excellent transparency. (2) The foreign matter in the polyester for fibers is a foreign matter which causes deterioration of strength in the fiber, and is a cause of contamination of the mold and the increase in the filtration pressure of the filter during the production of the yarn. In the manufacture of polyester fibers, in view of operability, it is desired to find a polyester polymerization catalyst which does not generate foreign matter. It has been tried to use antimony trioxide as a polycondensation catalyst, and to suppress the blackening of PET and the generation of foreign matter. For example, Patent No. 266 6 502 uses a compound of antimony trioxide, antimony and selenium as a polycondensation catalyst to suppress the formation of black foreign matter in PET. Further, JP-A-9-291141 discloses the use of antimony trioxide containing an oxide of sodium and iron as a polycondensation catalyst to suppress the formation of metal ruthenium. However, with such a polycondensation catalyst, it is impossible to achieve the purpose of reducing the ruthenium content. Although it has been proposed to use a titanium compound or a tin compound as a polycondensation catalyst other than a ruthenium compound, the polyester produced by such a film is easily deteriorated by heat during melt forming, and the polyester has a remarkable coloration. The problem point. Therefore, attempts have been made to overcome the problem of using a titanium compound as a polycondensation catalyst; for example, a method of simultaneously using a cobalt salt and a calcium salt of a tetraalkoxy titanate has been proposed by the Japanese Patent Publication No. 55-1 1 6722. Further, according to JP-A-8-7358, it is proposed to use a cobalt alkoxide titanate as a polycondensation catalyst and a method using a fluorescent whitening agent. However, when the tetraalkoxy titanate is used as a polycondensation catalyst according to such techniques, the coloration of PET cannot be lowered, and the effect of suppressing thermal decomposition of PET cannot be achieved. 1276646 V. Description of the invention (3) What the Ming compound knows is the poor activity of the catalyst. Among the ruthenium compounds, although it has been reported that, compared with other aluminum compounds as a polycondensation catalyst, the use of aluminum chelating compounds has higher catalytic activity; but it cannot be said that it is better than using the above. In the case of a ruthenium compound or a titanium compound, it has sufficient catalytic activity; in addition, when an aluminum compound is used as a polycondensation catalyst, it takes a long time to polymerize the polyester, and its thermal stability and thermal oxidation stability also change. The problem is poor. Moreover, when an aluminum compound is used as a polycondensation catalyst, a large amount of foreign matter insoluble to the polyester is generated, and the filter is clogged by the foreign matter during the molding of the polyester; and when the fiber is used, When spinning, it often causes breakage, and when used, it also has problems such as poor film properties. On the other hand, in the disclosure of the Japanese Patent Publication No. 46-4103, it is found that the alkali metal or a compound thereof and the aluminum chelating compound have excellent catalytic activity. When the polyester is polymerized according to the method described in the publication, the thermal stability is excellent, but the thermal oxidation stability is still poor. Further, a large amount of foreign matter insoluble to the polyester is formed, and the polyester is formed. When the fiber is used, the yarn is often broken during spinning, and the film property is deteriorated during use, and the like, and thus it is not practical. Although there is also a technique in which an alkaline earth metal compound is added to an aluminum compound to provide a catalyst having sufficient catalytic activity, in order to achieve practical catalyst activity, a large amount of an alkaline earth metal compound must be added, and the result will be The thermal stability and thermal oxidation stability of the polyester are deteriorated, so that the color of the insoluble foreign matter is increased as the color of the polyester is increased due to the heating of 1276646 and the invention (4). Although a ruthenium compound is used as a catalyst, it is possible to impart excellent catalyst activity other than a ruthenium compound, and it is possible to provide a polyester which does not have the above problems, and has been put to practical use, but such a catalyst also has a so-called very expensive problem. Further, there is a problem that the concentration of the catalyst in the reaction system changes due to easy distillation from the reaction system during polymerization, so that polymerization becomes difficult to suppress, and there is a problem in that it is used as a catalyst main component. Further, a method of suppressing thermal deterioration of the polyester at the time of melt molding is, for example, a method of removing a catalyst from a polyester. A method of removing a catalyst from a polyester is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. However, such a method of using a supercritical fluid is technically difficult, so that the cost of the product is also increased, which is not preferable. Based on the above various reasons, it is expected that a polymerization catalyst using a main metal component which uses a metal component other than cerium and lanthanum as a catalyst, and excellent catalyst activity, and which can impart heat deterioration without being caused by melt forming A polymerization catalyst for polyesters with excellent thermal stability. The polyester is decomposed by thermal decomposition during melt molding, and the molecular weight is lowered. Therefore, the heat resistance and mechanical properties of the melt-forming port are degraded, and the quality of the molded article is deteriorated by by-products of thermal decomposition, for example, coloring is increased. A known catalyst or a ruthenium catalyst can provide a polyester which is excellent in thermal stability during melt molding as compared with other titanium catalysts; however, thermal deterioration during melt molding cannot be completely prevented. In view of the above, it is expected that a kind of polyester polymerization catalyst which can strongly suppress the thermal deterioration at the time of melt-molding of a polyester is 1276646. A technique using an aluminum compound as a polymerization catalyst is proposed in WO 98/42769 and JP-A No. 1 1-507694. The aluminum compound may be, for example, an aluminum chelating compound such as acetonitrile aluminum acetate, an inorganic acid salt such as aluminum chloride or aluminum hydroxide, an aluminum salt of a carboxylic acid, or an aluminum alkoxide. Among them, an aluminum chelating compound such as aluminum acetate acetate is generally expensive, and the cost of the compound is lowered due to a decrease in the content of aluminum in the compound; or the solubility of a solvent such as ethylene glycol is lowered. The problem of adding methods is limited. Aluminium hydroxide or aluminum alkoxide or the like also has a problem that the solubility in the system is lowered, the catalytic activity is lowered, or the amount of insoluble foreign matter generated in the polyester is increased. The inorganic acid salt containing chlorine such as aluminum chloride has excellent catalyst activity, but also has a problem that the device is highly corrosive, or the color of the obtained polymer becomes large. On the one hand, aluminum salts of carboxylic acids such as aluminum acetate, basic aluminum acetate, aluminum lactate, and aluminum benzoate are generally inexpensive and have low corrosiveness to the device, but are low in solubility to polyester. At the same time, the activity on the catalyst is poor, so that not only the polyester produced may have a problem of turbidity, but also it may be a problem when used as a catalyst. For example, Japanese Lacquer No. 10-324747 No. 1 discloses that aluminum acetate used as a catalyst easily forms a foreign matter insoluble to polyester and causes a problem of poor spinnability. The object of the present invention is to provide an improved polyester and a method for producing the same, which use a metal component other than cerium and lanthanum as a catalyst. 1276646 5. Invention Description (6) Polymeric touch of metal component A polyester for producing a polyester and improving the clogging of the filter during molding, and a method for producing the same. Another object of the present invention is to provide a process for producing a polyester using a novel polymerization catalyst other than a ruthenium compound and a ruthenium compound, and a polyester produced by the method. Another object of the present invention is to provide a catalyst main component which does not contain a ruthenium compound or a ruthenium compound, which is excellent in catalytic activity, and which can suppress suppression in melt formation when the catalyst is deactivated or not removed. At the time of the thermal deterioration effect, a polymerization catalyst of a polyester excellent in thermal stability is obtained. The present invention also provides a method for improving the thermal stability during melt forming of a hollow molded article, a fiber, an engineering plastic or the like of a film, a bottle or the like by using the above-mentioned catalyst, and using a raw resin or recycling. The crumb can obtain a polyester of a high quality product; and a method of producing a polyester using the aforementioned polyester polymerization catalyst. Another object of the present invention is to provide a polyester polymerization catalyst which can provide a polyester which is extremely resistant to thermal deterioration during melt molding, and to form a hollow molded article such as a film or a bottle using the above-mentioned catalyst. The thermal stability during melt forming of fibers, engineering plastics, etc. is remarkably improved, and polyesters of high quality products can be obtained by using raw resin or by reusing the chips generated during molding; and using the aforementioned polyester polymerization touch The medium is used to make polyester. Another object of the present invention is to provide a catalyst main component which does not contain a ruthenium compound and a ruthenium compound, and which is inexpensive and has excellent catalytic activity. 1276646 5. Description of the invention (7) Less corrosion to the device, and more A polymerization catalyst capable of reducing the formation of polyester-insoluble foreign matter can be provided, and a method for producing the same. In addition, the present invention also provides a method for producing a polyester by using the above-mentioned catalyst, and a polyimide ester. [Inventors of the Invention] The present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, found that an alkali metal compound is used. Or the cause of the polyester-insoluble foreign matter formed during the polymerization of the alkaline earth metal compound or the catalyst coexisting with the aluminum compound, mainly due to the alkali metal compound or the alkaline earth metal compound, and is also found to be caused by the polyester When the content of the alkali metal compound, the soil-measuring metal compound, and the aluminum compound is within a specific range, it will have an inhibitory effect on the formation of a foreign substance insoluble to the polyester, and improve the problem of the filter clogging during the molding of the polyester. The present invention has been completed. In other words, the present invention provides a polyester which solves the above-mentioned problems, characterized in that the polyester contains at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof, and At least one selected from the group consisting of white aluminum and a compound thereof, and the content thereof satisfies the following formulas (1) and (2): (1) "M" <0.05; (2) "M" / (A1» ^ 20 ; (in the formulas (1) and (2), "Μ" represents an alkali metal atom and a soil test metal relative to the acid component of the polyester.旲 % % 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 As a result, it was found that the use of an alkali metal compound or an alkaline earth metal compound and a catalyst coexisting with the aluminum compound is a cause of formation of a foreign substance insoluble in the polyester during polymerization, and further examination revealed that when coexisting with the phosphorus compound There is an effect of reducing foreign matter, and it is found that by making the content of the above-mentioned metal compound or phosphorus compound in the polyester within a specific range, it is possible to suppress the formation of foreign matter insoluble to polyester and to improve the formation of polyester. The present invention has been made in view of the problems such as clogging of the filter, etc. It is intended that the present invention provides a polyester which can solve the above problems, characterized in that the polyester contains an alkali metal and its At least one selected from the group consisting of alkaline earth metals and compounds thereof, at least one selected from the group consisting of aluminum and its compounds, and at least one selected from the group consisting of phosphorus compounds One, and its content satisfies the following formulas (4) to (6): (4) 0.1 ^ [M] ^ 150 ;. (5) [M] / [A1] ^ 40 ; (6) [P] / [A1] ^ 0.01; (In the formulae (4) to (6), [M] represents the total amount (ppm) of the alkali metal atom and the alkaline earth metal atom contained in the polyester; [A1] and [P] The amount of the aluminum atom and the phosphorus atom (ppm) contained in the polyester is represented by the present inventors. The inventors of the present invention have conducted an intensive review based on the object of solving the above problems, and found that an alkali metal compound or an alkaline earth metal is used. The compound and the catalyst coexisting with the aluminum compound form a foreign matter insoluble to the polyester during polymerization, and the main cause is an alkali metal compound and an alkaline earth metal compound-10-1276646. 5. Description of the invention (9); The results of the review revealed that the use of alkali metal compounds or alkaline earth metal compounds contained lithium, sodium, potassium, At least one selected from the group consisting of strontium, magnesium, calcium and a compound thereof, and the content thereof in the polyester is within a specific range, and further, when coexisting with the phosphorus compound, the effect of reducing foreign matter formation is improved and improved The present invention has been made in view of the problem that the filter is clogged during the molding of the polyester. The method for solving the above problems of the present invention provides a polyester and a method for producing the same, characterized in that the polyester contains lithium, At least one selected from the group consisting of sodium, potassium, barium, magnesium, calcium, and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof, and a group consisting of phosphorus compounds At least one selected is selected, and the total content of lithium, sodium, potassium, sensitized, magnesium, 15 and its compounds is 7.0 moles or less per 106 grams of the polymer in terms of metal atoms. In addition, the inventors of the present invention conducted a review based on the object of solving the above problems, and found that a polyester produced by using a catalyst having a main metal component of an aluminum compound and containing a group selected from the group consisting of phosphorus compounds At least one and at least one selected from the group consisting of phenol-based compounds, and the content of phosphorus atoms and aluminum atoms in a specific range, is a problem of improving filter clogging during forming and thermal oxidation. The invention is achieved by the stability of the object. That is, the method for solving the above problems of the present invention provides a polyester and a method for producing the same, characterized in that the polyester contains at least one selected from the group consisting of aluminum and a compound thereof, and self-phosphating -11- 1276646 5. Invention (1〇) At least one selected from the group consisting of: and at least one selected from the group consisting of phenolic compounds, and the content of phosphorus atoms in the polyester The ratio of (ppm) to the content of aluminum atoms (ppm) is in the range of 0.01 to 50. In addition, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that a catalyst made of an aluminum compound generates a foreign substance insoluble in polyester when polymerized, and is mainly an aluminum compound; Further, it was found that when the aluminum compound and the phosphorus compound coexist in the polyester, and the specific ratio of the aluminum compound to the phosphorus compound is 値, the effect of reducing the foreign matter is improved, and the problem of the filter clogging during the molding of the polyester is improved. And the invention is achieved. That is, the method of the present invention for solving the above problems is to provide a polyester characterized in that the polyester contains at least one selected from the group consisting of aluminum and a compound thereof, and a group composed of a self-phosphorus compound. At least one selected from the group, and the ratio of the content of the phosphorus atom (ppm) to the content of the atom (ppm) in the polyester is in the range of 0.5 to 20. Further, the present invention provides the above polyester produced by using a catalyst made of the above metal and/or compound, and a method for producing the same. In addition, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that although the catalytic activity of the aluminum compound is inferior, sufficient activity can be obtained by combining with a phosphorus compound as a catalyst. Thus, the present invention has been achieved. When the polymerization catalyst of the present invention is used, a polyester excellent in quality without using a ruthenium compound can be obtained inexpensively. -12- 1276646 V. INSTRUCTION DESCRIPTION (11) That is, the method for solving the above problems of the present invention provides a method for producing a polyester, which is characterized in that, in the production of a polyester, it is composed of aluminum and a compound thereof. At least one selected from the group consisting of at least one selected from the group consisting of phosphorus compounds, and the ratio of the added phosphorus atom to the aluminum atom is in the range of 0.5 to 20; and a The polyester produced by the method. Further, the present invention provides a polymeric polyester catalyst characterized in that the polyester is at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus compounds. One is constituted, and the ratio of the phosphorus atom to the aluminum atom is in the above-mentioned range; and the polyester produced using the same, and the method for producing the polyester are provided. In addition, the inventors of the present invention have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that although the catalytic activity of the metal or gold compound itself is poor, combination with a phosphorus compound can increase the activity of the catalyst. An ester polymerization catalyst, which is a polyester polymerization catalyst composed of a metal, a metal compound, and a phosphorus compound, which is excellent in catalytic activity, and is capable of imparting inhibition to melt formation when the catalyst is deactivated or not removed. In the case of the thermal deterioration effect at the time, a polymerization catalyst of a polyester excellent in thermal stability is obtained, and the present invention has been completed. That is, the method for solving the above problems of the present invention provides a polyester polymerization catalyst characterized in that the polyester polymerization catalyst is composed of a metal or a metal compound and a phosphorus compound, and the activity parameter (AP) ) satisfy the following formula (10); (10) AP (minutes) < APX (分); -13- 1276646 V. Description of Invention (12) (In the above formula, AP represents a polymerization property at a pressure of 275 ° C, 0.1 Tory using a predetermined amount of catalyst. The time (minutes) required for polyethylene terephthalate (PET) having a viscosity of 0.65 dl/g; APX means that only the above metal or metal compound is polymerized under the same conditions and under the same conditions as above. The time (minutes) required for PET). Further, the present invention provides a polyester polymerization catalyst characterized in that the polyester polymerization catalyst is used for polymerizing polyethylene terephthalate having a thermal stability parameter (TS) satisfying the following formula (9) (PET). The thermal stability during melt molding of a hollow molded article such as a film or a bottle formed of a polyester polymerized by the polyester polymerization catalyst, a fiber, an engineering plastic, or the like can be remarkably improved, and a raw resin is used. Or, by using the debris generated during molding, a product having excellent quality can be obtained. (9) TS <0.20; (In the above formula, TS is a test in which 1 g of PET having an intrinsic viscosity ([IVh) of 0.64 to 0.66 dl/g is placed in a test tube, and dried at 130 ° C for 12 hours under vacuum, and is not circulated. Under the nitrogen atmosphere, after maintaining the melting at 300 ° C for 2 hours, the following formula is used to calculate the characteristic viscosity ([IV]f ); TS = 0.245 { [IV], 1.47 - [IVh·1.47} PET with a viscosity of 0.64~0.66 dl / gram can actually measure the stirring torque of the PET polymerization vessel and the correlation with the characteristic viscosity to manage the stirring torque of the polymerization state, and make the stirring torque reach the predetermined値 Seasonal aggregation is stopped and obtained. Further, the inventors of the present invention have intensively reviewed the purpose of improving the catalytic activity of the aluminum carboxylate salt, and found that the aluminum salt of the carboxylic acid is previously dissolved in water or an organic solvent. The catalyst made by the substance will increase the activity of the catalyst, and the proposal of the present invention is obtained. That is, the method for solving the above problems of the present invention provides a polyester polymerization catalyst characterized in that the polyester polymerization catalyst is dissolved by at least one selected from the group consisting of aluminum carboxylates. A solution formed in water and/or an organic solvent; and a method of making the solution. BEST MODE FOR CARRYING OUT THE INVENTION The polyester of the present invention must be at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof; And the molar content of all the constituent units of the carboxylic acid component such as a polyvalent carboxylic acid, the total content of the metal atoms is less than 〇·〇5 mol%. Further, it is preferably at least 0.005 mol%. When the content is 0.05 mol% or more, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, the resin is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the problem that the hydrodegradability of the resin is deteriorated also occurs. When the content is less than 0.005 mol%, there is a problem that the thermal stability of the resin is insufficient, and at the same time, in the case of being used as a catalyst, the catalytic activity is remarkably lowered; thus, it is not preferable. A preferred range of content is from 0.008% to 0.03 mole%; more preferably in the range of 0.01 mole% to 0.02 mole%. -15- 1276646 V. INSTRUCTION DESCRIPTION (14) The polyester of the present invention must be at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, and added to aluminum and its compounds. At least one selected from the group consisting of. Further, the alkali metal is at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. The total amount of atoms and alkaline earth metal atoms must be below 20 with the molar ratio of aluminum atoms. Further, it is preferably 0.1 or more. When the ratio of the lanthanum exceeds 20, a large amount of foreign matter insoluble in the polyester is generated, and as a result, the yarn is frequently broken during spinning, or the so-called filter clogging is caused during molding. Further, when it is used as a catalyst, there is a problem that the so-called catalyst activity is remarkably lowered. When the specific enthalpy is less than 0·1, a large amount of foreign matter which is insoluble to the vinegar due to the aluminum compound is generated, and the thermal stability of the resin is deteriorated, which is not preferable. The preferred range for comparison is from 0.5 to 10. When at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof in the polyester, and at least one selected from the group consisting of the self-existing compound and the compound thereof, In the range, it has an effect of suppressing foreign matter insoluble in polyester, and improves problems such as breakage at the time of spinning or clogging of the filter at the time of molding. Further, the content of the aluminum and the compound thereof of the present invention is preferably from 0.001 mol based on the number of moles of all constituent units of the carboxylic acid component of the dicarboxylic acid and the polycarboxylic acid in the polyester. % to 〇〇5% of the range. When the aluminum atom content exceeds 0.05 mm%, the heat of the resulting polyester is -16-1276646. 5. The invention (15) stability is deteriorated, and thus it is not preferable. When the aluminum atom content is 0.001 mol% or less, when used as a catalyst, the catalytic activity is remarkably lowered, which is not preferable. A preferred range of content is from 0.005 mol% to 0.04 mol%; more preferably in the range of 0.01 mol% to 0.03 mol%. The total amount of alkali metal atoms and alkaline earth metal atoms contained in the polyester of the present invention is preferably 25 ppm or less from the viewpoint of reducing foreign matter. This content is preferably below 20 ppm, more preferably below 15 ppm. Further, in the polyester of the present invention, at least one selected from the group consisting of the above-mentioned alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof is required; however, since it contains an alkaline earth metal and The polyester of the compound has poor thermal stability, is colored in a large amount by heating, and has a large amount of foreign matter generated. Therefore, in the polyester of the present invention, it is preferred to contain no alkaline earth metal and a compound thereof, but an alkali metal. . Further, the polyester of the present invention is preferably a phosphorus compound. When a phosphorus compound is contained, the effect of suppressing foreign matter derived from an alkali metal or an alkaline earth metal can be obtained, and the thermal stability of the polyester can be improved. According to the above, the polyester containing aluminum and its compounds, and the alkaline earth metal and the compound thereof tend to have poor thermal stability, and the generation of foreign matter is relatively large; however, the alkaline earth metal contained in the scope of the present invention is Further, when a phosphorus compound is contained, the problem of thermal stability and foreign matter of the polyester can be improved. According to the method of the present invention, when a phosphorus compound is added in the production of a polyester, it is preferable to have an effect of suppressing generation of a foreign substance insoluble in polyester. Further, it is preferable to increase the thermal stability of the polyester by the addition of the phosphorus compound ' -17-1276646 5 and the invention (16). The amount of the phosphorus compound used in the present invention is preferably from 5 X to 10·5 based on the number of moles of all the constituent units of the carboxylic acid component such as the dicarboxylic acid and the polycarboxylic acid in the obtained polyester. The range of % to 1% of the ear; more preferably in the range of from 1 X 1 〇 4 mol% to 0.5 mol %. Further, the additional polyester of the present invention must be at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and compounds thereof; the total content of metal atoms in the polyester is 0. 1 ppm or more and 150 ppm or less. When the content is more than 150 ppm, a large amount of foreign matter insoluble to the polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, there is a problem that the color of the resin becomes conspicuous, the appearance of the molded article is deteriorated, and the thermal stability of the resin and the hydrodegradability are lowered. When the content is less than 0.1 ppm, the problem of lack of thermal stability of the resin occurs. In the case of use as a catalyst, there is a problem that the so-called catalyst activity is remarkably lowered. The preferred range is from 1 ppm to 100 ppm; more preferably from 5 ppm to 50 ppm. The polyester of the present invention must be at least one selected from the group consisting of the above-mentioned alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. . Further, the alkali metal is at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. Atomic and alkaline earth gold-18- 1276646 V. Description of invention (17) The total atomic weight (ppm), and the content of aluminum atoms (ppm) must be below 40. Further, the ratio is preferably 0.05 or more. When the ratio is more than 40, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage occurs frequently during spinning, or so-called filter clogging occurs during molding. Further, when it is used as a catalyst, there is a problem that the so-called catalyst activity is remarkably lowered. When the specific enthalpy is less than 〇.〇5, a large amount of foreign matter insoluble to the polyester due to the aluminum compound is generated, and the thermal stability of the resin is deteriorated, which is not preferable. The preferred range of the enthalpy is 0.1 or more and 20 or less, more preferably 0.5 or more and 10 or less. The polyester of the present invention must be at least one selected from the group consisting of the above-mentioned alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. And adding at least one selected from the group consisting of phosphorus and a compound thereof. Further, the phosphorus atom is at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. The ratio of the content (ppm) to the aluminum atom content (ppm) must be 0.01 or more. Further, the ratio is preferably 30 or less. When the specific enthalpy is less than 0 · 01, a large amount of foreign matter insoluble to the polyester due to the aluminum compound is generated, and the thermal stability of the resin is deteriorated, which is not preferable. When the ratio is more than 30, a large amount of foreign matter insoluble to polyester is generated; and when it is used as a catalyst, a problem that the so-called catalyst activity is remarkably lowered may occur. The preferred range for comparison is from 0 to 1 to 20, more preferably from 1 to 1 〇. -19- 1276646 V. INSTRUCTION DESCRIPTION (18) In the polyester of the present invention, at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, and from aluminum At least one selected from the group consisting of a compound thereof, and at least one selected from the group consisting of phosphorus and a compound thereof; having an effect of suppressing generation of a foreign matter insoluble to the polyester, and improving the spinning Problems such as broken wires or blocked filters during forming. Further, in the aluminum of the polyester of the present invention and the compound thereof, the range of the aluminum atom contained in the polyester is preferably 0.5 ppm or more and 500 ppm or less. When the content of the aluminum atom exceeds 500 ppm, a large amount of foreign matter insoluble to the polyester is generated, and the problem of lack of thermal stability of the resin occurs, which is not preferable. When the aluminum atom content is less than 0.5 ppm, a large amount of foreign matter due to alkali metals and alkaline earth metals is generated, and when used as a catalyst, catalytic activity is remarkably lowered, which is not preferable. The preferred range is from 5 ppm to 70 ppm; more preferably from 10 ppm to 30 ppm. Further, in the phosphorus compound of the present invention, the content of the phosphorus atom in the polyester is preferably in the range of 1 ppm or more and 100 ppm or less. When the content of the phosphorus atom is less than 1 ppm, the effect of suppressing the formation of the insoluble foreign matter of the polyester is lacking, and the thermal stability of the polyester is deteriorated, which is not preferable. When the content of the phosphorus atom exceeds 1 000 ppm, a large amount of polyester-insoluble foreign matter is generated, which is not preferable. The preferred range is from 10 ppm to 200 ppm; more preferably from 20 ppm to 100 ppm. In the polyester of the present invention, it is necessary to contain at least one selected from the group consisting of alkali metals and their compounds -20-1276646, invention description (19), and alkaline earth metals and compounds thereof, and from aluminum and At least one selected from the group consisting of compounds, but in terms of reducing foreign matter in the polyester and reducing the coloration of the polyester, it is preferable to contain lithium, sodium, potassium, rubidium, magnesium. At least one selected from the group consisting of calcium and its compounds. Among them, at least one selected from the group consisting of lithium, calcium and a compound thereof is preferred because it has excellent thermal stability of the polyester. Further, in terms of reducing the coloration of the polyester, it is preferred to contain at least one selected from the group consisting of calcium and a compound thereof. The present invention relates to a polyester obtained by using a catalyst made of the above metal and/or compound, and a method for producing the same. The amount of the metal and/or compound to be added must be such that the metal atom content in the finally obtained polyester is as described above. The polyester obtained by this method is a problem in which the effect of suppressing the formation of a polyester-insoluble foreign matter is improved, the yarn is broken during spinning, or the filter is clogged during molding. The alkali metal and its compound used in the present invention as a polymerization catalyst, and an alkaline earth metal and a compound thereof are preferably used from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba. At least one selected; in which an alkali metal or a compound thereof is used, since the polyester which is insoluble to the polyester is reduced, the thermal stability of the polyester is also excellent, which is preferable. In the case of using an alkali metal or a compound thereof, it is preferred to use Li, Na, K and a compound thereof. Among these, in order to reduce the foreign matter insoluble to the polyester, it is more preferable to use Li and a compound thereof. -21 - 1276646 V. DESCRIPTION OF THE INVENTION (2) Further, another polyester of the present invention is characterized in that it contains a group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium and a compound thereof. At least one selected from the group consisting of at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus and a compound thereof; and lithium, sodium, potassium, rubidium, magnesium, calcium The total content of the compound and its compound is 7.0 moles or less per 106 grams of the polymer in terms of metal atoms. When the content is more than 7.5 mol, a large amount of foreign matter insoluble to the polyester is generated, and as a result, yarn breakage occurs frequently during spinning, or a so-called filter clogging occurs during molding. Further, the resin is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the hydrodegradability of the resin is deteriorated. The content is preferably 0.05 mol or more; when the content is less than this, the problem of lack of thermal stability of the resin occurs, and when used as a catalyst, the catalytic activity is remarkably lowered. The preferred content range is 0.1 to 4.0 m; more preferably 0.2 to 2. 5 m; particularly ideal is 0. 2 to 1. 2 m. Such a polyester is one which has an effect of suppressing the generation of insoluble foreign matter in the production of polyester, a problem of yarn breakage during spinning, or clogging of the filter during molding. The content of aluminum and its compound in the polyester of the present invention is preferably 0.5 to 500 ppm in terms of aluminum atom. When the content of the atom is more than 500 ppm, not only a large amount of the polyester-insoluble foreign matter due to the aluminum atom but also a problem of lack of thermal stability of the resin may occur, which is not preferable. When the aluminum atom content is less than 0.5 ppm, a large amount of foreign matter due to alkali metal and alkaline earth metal is generated, and when it is used as a catalyst, it may occur. -22 - 1276646 5. Description of invention (21) The media activity is significantly reduced and therefore not suitable. The preferred content range is from 5 to 70 ppm; more preferably from 10 to 40 ppm; particularly preferably from 15 to 25 ppm. The content of phosphorus and its compound in the polyester of the present invention is preferably from 1 to 1000 ppm in terms of phosphorus atom. When the content of the phosphorus atom is less than 1 ppm, not only the effect of suppressing the formation of insoluble foreign matter to the polyester but also the thermal stability of the resin is lowered, which is not preferable. When the content of the phosphorus atom exceeds 1 000 ppm, a large amount of insoluble foreign matter due to the aluminum atom is generated, which is not preferable. The preferred content range is from 10 to 200 ppm; more preferably from 20 to 100 ppm. In the polyester of the present invention, at least one selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium and a compound thereof must be contained; however, according to the reduction of foreign matter in the polyester, and the reduction of the polyester From the viewpoint of coloring, it is preferable that at least one selected from the group consisting of lithium, sodium, magnesium, calcium, and a compound thereof. Among them, it is preferred to contain at least one selected from the group consisting of lithium, sodium and a compound thereof. The present invention relates to a method for producing a polyester using a catalyst, wherein the catalyst used contains at least one selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium, and a compound thereof, and At least one selected from the group consisting of aluminum and its compounds, and the content thereof is in the above range with respect to the polyester finally obtained. The polyester obtained by this method is a problem in which the effect of suppressing the formation of a polyester-insoluble foreign matter is improved, the yarn is broken at the time of spinning, or the filter is clogged during molding. -23- 1276646 V. Inventive Note (22) Further, another polyester of the present invention contains at least one selected from the group consisting of aluminum and a compound thereof, and a group consisting of self-phosphorus compounds At least one selected from the group consisting of at least one selected from the group consisting of phenolic compounds; and the ratio of the amount of phosphorus atoms (ppm) contained in the polyester to the amount of aluminum atoms (ppm) Niobium (amount of phosphorus atom/amount of aluminum atom) is in the range of 0.01 to 50. When the ratio of the amount of the phosphorus atom (ppm) to the amount of the aluminum atom (ppm) is 値 (the amount of phosphorus atom/amount of aluminum atom) is 0.01 hour; a large amount of foreign matter insoluble to the polyester is generated, and as a result, the spinning is frequently performed. Problems such as so-called filter clogging occur when a broken wire occurs or when it is formed. Further, the resin is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the problem that the hydrolysis resistance of the resin is deteriorated also occurs. When the specific enthalpy exceeds 50, a large amount of foreign matter insoluble to the polyester is generated, and as a result, the yarn breakage frequently occurs during spinning, or a so-called filter clogging occurs during molding. Moreover, when used as a catalyst, the catalytic activity is remarkably lowered. The preferred content range is from 0.1 to 20; more preferably from 0.5 to 10. The content of aluminum and its compound in the polyester of the present invention is preferably 0.5 to 500 ppm in terms of aluminum atom. When the content of the atom is more than 500 ppm, not only a large amount of the polyester-insoluble foreign matter due to the aluminum atom but also a problem of lack of thermal stability of the resin may occur, which is not preferable. When the aluminum atom content is less than 0.5 ppm, when used as a catalyst, catalytic activity is significantly lowered, which is not preferable. The preferred content range is from 5 to 70 ppm; more preferably from 10 to 40 ppm; particularly preferably from 15 to 25 ppm. 24 1276646 V. INSTRUCTION OF THE INVENTION (23) The polyester of the present invention has an effect of enhancing the catalytic activity of an aluminum compound by containing a phosphorus compound, and suppresses the occurrence of foreign matter, and improves the heat of the polyester. Stability, and thermal oxidation stability. Further, by containing a phenol-based compound, the thermal oxidation stability of the polyester is further increased by one layer, and as a result, thermal deterioration and yellowing of the polyester can be suppressed. Further, another polyester of the present invention is characterized in that it contains at least one selected from the group consisting of phosphorus compounds, and at least one selected from the group consisting of phenolic compounds. The ester; and the total amount of metal atoms contained in the polyester is 1 〇〇 ppm or less based on the polyester. The polyester is a problem in which a so-called filter clogging is caused when the molding is improved, and the heat stability and thermal oxidation stability are improved. When the total amount of metal atoms exceeds 100 ppm, the foreign matter in the polyester increases and the quality of the polyester is deteriorated, which is not preferable. When the total amount of metal atoms contained in the polyester is 1 ppm or more, when such a metal is used as a catalyst, catalytic activity can be exhibited, which is preferable. The total amount of metal atoms is preferably 3 to 50 ppm; more preferably 5 to 30 ppm. The metal species is not particularly limited, but it is preferably one or more selected from the group consisting of alkali metals, alkaline earth metals, and aluminum. The content of phosphorus and its compound in the polyester of the present invention is preferably from 1 to 1000 ppm in terms of phosphorus atom. When the content of the phosphorus atom is less than 1 ppm, not only the effect of suppressing the formation of insoluble foreign matter to the polyester but also the thermal stability of the resin is lowered, which is not preferable. When the content of the phosphorus atom exceeds 1 〇〇〇 ppm, a large amount of the polyester-insoluble foreign matter due to the aluminum atom is generated, which is not preferable because it is -25- 1276646. The preferred content range is from 10 to 200 ppm; more preferably from 20 to 100 ppm. On the other hand, in order to increase the physical properties such as thermal stability of the polyester, it is preferred that the polyester of the present invention is selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds. At least one. In view of reducing the foreign matter in the polyester and reducing the coloration of the polyester, it is preferable that at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, and a compound thereof. Among these, at least one selected from the group consisting of lithium, calcium and a compound thereof is preferred because it has excellent polyester thermal stability. Further, it is preferable to contain at least one selected from the group consisting of calcium and a compound thereof in view of reducing the coloration of the polyester. In the case where the polyester of the present invention contains an alkali metal, an alkaline earth metal, and a compound thereof, the content thereof is preferably from 1 X 10·6 or more to the number of moles of all the polycarboxylic acid units constituting the polyester. Less than 0·1 mol%; more preferably 5 X 10·6~0.05 mol%; more preferably 1 X 10·5~〇·〇3 mol%; particularly suitable from 1 X 1 (Γ5~ 〇· 〇1 mol%. When the content of alkali metal or alkaline earth metal is small, it can reduce the deterioration of thermal stability, decrease in hydrodegradability, and cause problems such as foreign matter and coloration. When alkali metals, alkaline earth metals and When the content of the compound is 0.1 mol% or more, the thermal stability is deteriorated, foreign matter is increased, coloring is increased, and hydrodegradability is lowered, and the product is processed. When the content is less than 1 X 10·6 mol In the case of %, the effect of the inclusion is not clear. -26- 1276646 V. INSTRUCTION DESCRIPTION (25) The present invention relates to a method of producing a polyester as described above using a catalyst made of the above compound. Another type of polyester must be a group consisting of aluminum and its compounds. At least one selected from the group consisting of phosphorus and a compound thereof; and the ratio of the phosphorus atom content (ppm) to the aluminum atom content (ppm) in the polyester must be 0.5 to 20 When the specific enthalpy is less than 0.5, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, the resin is significantly colored. When the problem of the appearance of the molded article is broken, the problem that the hydrodegradability of the resin is deteriorated may occur. When the specific enthalpy exceeds 20, a large amount of foreign matter insoluble to the polyester is generated, and as a result, at the time of spinning Frequent occurrence of yarn breakage or formation of so-called filter clogging during molding. Further, when used as a catalyst, there is a problem that the catalytic activity is remarkably lowered. The preferred range is 1 to 1 5 More preferably, it is 3 to 10 Å in the polyester of the present invention, at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus and a compound thereof. One Further, since the content is in the above range, it has an effect of suppressing generation of foreign matter insoluble in polyester, and can improve problems such as yarn breakage during spinning or clogging of the filter during molding. The content of the compound is preferably in the range of from 1 to 100 ppm in terms of the aluminum atom in the polyester. When the content of the saturated atom exceeds 100 ppm, not only a large amount of the aluminum atom is not produced, but the polyester is not -27- 1276646. V. INSTRUCTIONS (26) Dissolved foreign matter, and the problem of lack of thermal stability of the resin may occur, which is not good. When the aluminum atom content is less than 1 ppm, it may come into contact when used as a catalyst. The media activity is significantly reduced and therefore not suitable. Preferably, it is in the range of 5 ppm or more and 70 ppm or less; more preferably in the range of 1 〇 ppm or more and 30 ppm or less. Further, the content of the phosphorus compound of the present invention is preferably in the range of 5 ppm or more and 200 ppm or less in terms of the phosphorus atom in the polyester. When the content of the phosphorus atom is less than 5 ppm, the effect of suppressing the formation of the insoluble foreign matter of the polyester is lacking, and the thermal stability of the polyester is deteriorated, which is not preferable. When the content of the phosphorus atom exceeds 200 ppm, a large amount of polyester-insoluble foreign matter is generated, which is not preferable. The preferred range is from 10 ppm to 100 ppm • and more preferably from 20 ppm to 80 ppm. The presence of the phosphorus compound in the polyester of the present invention is not particularly limited, but it is preferred to use a phosphonic acid compound, a phosphinic acid compound, or a phosphine oxide system. Any of a compound, a phosphonous acid compound, a phosphinous acid compound, and a phosphine compound. In the case of polymerizing a polyester, the use of a phosphorus compound having such a structure in combination with an aluminum compound has an effect of increasing the activity of the catalyst. Among these, when a catalyst made of a phosphonic acid-based compound is used, the effect of increasing the catalytic activity is increased, which is preferable. Among the phosphonic acid compounds, in order to increase the effect of increasing the activity of the catalyst, it is preferred to use a structure having an aromatic ring as a catalyst. -28- 1276646 V. Inventive Note (27) Further, on the one hand, in order to increase the physical properties such as thermal stability of the polyester, it is preferred to contain the alkali metal and its compound, and the alkaline earth metal in the polyester of the present invention. At least one selected from the group consisting of compounds. In view of reducing the foreign matter in the polyester and reducing the coloration of the polyester, it is preferable that at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, and a compound thereof. In the case where the polyester of the present invention contains an alkali metal, an alkaline earth metal, and a compound thereof, the content thereof is preferably from 1 X 10 6 or more to less than 0.1 based on the number of moles of all polycarboxylic acid units constituting the polyester. Molar%; more preferably 5 X 10·6~0.05 mol%; more preferably 1 X 10·5~〇·〇3 mol%; particularly suitable from 1 X 10·5~0.01 mol% . When the content of the alkali metal or the alkaline earth metal is small, the thermal stability is deteriorated, the hydrodegradability is lowered, and foreign matter or coloration is caused. When the content of the alkali metal, the alkaline earth metal, and the compound thereof is at least 0.1% by mole, the thermal stability is deteriorated, foreign matter and coloring are increased, and hydrostatic decomposition resistance is lowered. When the content is less than 1 X 1 〇 6 mol%, the effect is not clear. The present invention relates to a polyester obtained by using a catalyst made of the above metals and compounds, and a method for producing the same. The amount of the metal and/or compound to be added must be such that the content of the metal atom and the phosphorus atom in the finally obtained polyester is as described above. By this method, the effect of suppressing the formation of polyester-insoluble foreign matter is suppressed, the yarn is broken during spinning, or the filter is clogged during molding. The polyester of the present invention is preferably produced by using a polymerization catalyst made of a ruthenium compound, a ruthenium compound, titanium -29-1276646, a description (28) compound, a tin compound or the like. Further, in the case where the polymerization catalyst used in the polyester of the present invention is used in combination with a polymerization catalyst such as a ruthenium compound, a ruthenium compound, a titanium compound or a tin compound, the addition amount of the components is added. It is preferable that the problem of the product such as the characteristics, workability, color tone, and the like of the polyester as described above is not caused, the polymerization time is shortened, and the productivity is effectively improved. When the content of the ruthenium atom in the polyester of the present invention is 50 ppm or less based on the amount of the polyester, the polyester is not blackened and the occurrence of foreign matter is suppressed, which is preferable. Preferably it is below 30 ppm, more preferably below 10 ppm. On the other hand, in the polyester of the present invention, it is preferred that the content of the ruthenium atom in the polyester of the present invention is not contained, and the amount of the ruthenium atom in the polyester of the present invention will not be cost when the amount is less than 20 ppm with respect to the polyester. The above disadvantages are preferred. Preferably it is below 10 ppm, more preferably below 5 ppm. On the other hand, it is preferred that the polyester of the present invention contains no germanium atoms. When the content of the titanium atom in the polyester of the present invention is 5 ppm or less based on the amount of the polyester, the polyester has excellent heat stability and color tone, which is preferable. It is preferably at least 3 ppm, more preferably at most 1 ppm. On the other hand, the polyester of the present invention preferably contains no titanium atoms. Further, in view of reducing the coloring of the polyester, it is preferred that the polyester of the present invention contains cobalt and a compound thereof. However, the content of cobalt and its compound in the polyester should preferably be less than 10 ppm relative to the polyester. It is preferably less than 5 ppm, more preferably less than 3 ppm. -30- 1276646 V. INSTRUCTIONS (29) It is known that the cobalt compound itself has catalytic activity, and when the degree of addition is such that the catalytic effect is fully exerted, the transparency of the obtained polyester polymer is lowered, and heat is obtained. Stability is worse. In the present invention, by adding a small amount of a cobalt compound as described above so as to make the effect of the catalyst unclear, the transparency of the polyester polymer having the elimination is lowered, and the thermal stability is deteriorated, and the coloring is eliminated. effect. Further, the cobalt compound in the present invention has an object of elimination, and the addition period is preferably at the stage of polymerization, and it does not matter after the end of the polymerization reaction. On the other hand, in order to improve the thermal stability and transparency of the polyester polymer, the polyester of the present invention preferably does not contain a cobalt atom. Further, another polyester polymerization catalyst of the present invention is characterized in that it is at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus compounds. The composition is such that the ratio of the phosphorus atom to the aluminum atom is in the range of 0·5 to 20. The method for producing a polyester according to the present invention, which is characterized in that it is at least one selected from the group consisting of aluminum and a compound thereof in the above range, and at least one selected from the group consisting of phosphorus compounds. . When the molar ratio is less than 〇.5, the catalytic activity is significantly lowered, and thus it takes more time than the polymerization of the polyester of the predetermined viscosity. The preferred range of the molar ratio is 2 to 15; more preferably 3 to 1 0; particularly suitable is 4 to 8. The amount of the compound and its compound added in the present invention is preferably from 1 to 0.1 mol% based on the atomic weight of the aluminum based on the number of moles of all the polycarboxylic acid units constituting the polyester. When the amount added exceeds 0.1 mol%, the thermal stability and thermal oxidation stability of the polyester-31 - 1276646, the invention description (3〇) are deteriorated, and the stomach and color of the polyester are insoluble. Increase the problem. When the content is less than 0 · 〇〇 1 mol%, the shell U cannot sufficiently exert the activity of the catalyst. A preferred addition amount range is 0.003 mol% to 0.05 mol%; more preferably 0.005 mol% to 〇〇2 ng%; particularly suitable is 0.007 mol% to 0.015 mol%. Such a small amount of the aluminum component added to the polymerization catalyst of the present invention has a large characteristic which exhibits sufficient catalytic activity characteristics. As a result, the thermal stability and thermal oxidation stability are improved, and the foreign matter caused by aluminum and the coloring amount of the phosphorus compound in the present invention are reduced, and the number of moles of all the polycarboxylic acid units constituting the polyester is reduced. Preferably, it is 0.005 mol% to 0.2 mol% based on the phosphorus atom. When the amount added is less than 0.005 mol%, the effect of addition cannot be sufficiently exerted. When the amount added exceeds 0.2 mol%, the catalytic activity is lowered in the case of a polyester polymerization catalyst. The preferred addition amount range is 0.007 mol% to 0.05 mol%; more preferably 〇.〇1 mol%~0.02 mol%. A technique in which an aluminum compound is mainly used as a catalyst component without using a phosphorus compound, although it is possible to prevent the use of an aluminum compound as a main catalyst component by reducing the amount of the compound used, and to reduce the thermal stability. The technique of coloring, but when the degree of addition is such that the cobalt compound has sufficient catalytic activity, the thermal stability is deteriorated. Therefore, there is a technical difficulty in making both of them both. According to the present invention, by using a specific amount of a phosphorus compound, -3 2- 1276646 5. The invention (31) does not cause problems such as a decrease in thermal stability and generation of foreign matter, but a metal-containing property is obtained. The addition amount of the aluminum component is a small amount of a polymerization catalyst having a sufficient catalytic effect; by using such a polymerization catalyst, it is possible to improve the melt molding of a hollow molded product such as a polyester film or a bottle, a fiber or an engineering plastic. The heat stability of the time. In the phosphorus compound of the present invention, it is not preferable to add an effect of adding a phosphate such as phosphoric acid or trimethylphosphoric acid. Further, in the range of the amount of the phosphorus compound of the present invention to be added in the present invention, it may be used in combination with a polyester polymerization catalyst containing a metal such as a ruthenium compound, a titanium compound, a tin compound or a ruthenium compound, but the promotion cannot be confirmed. The effect of the melt polymerization. Further, another feature of the present invention is a polyester polymerization catalyst characterized in that the catalyst is used for polymerizing polyethylene terephthalate having a thermal stability parameter (TS) satisfying the following formula (9) Ester (PET); (9) TS <0.20; (However, TS is a non-circulating nitrogen atmosphere in which 1 gram of PET having an intrinsic viscosity ([IVh) of 0.64 to 0.66 dl / gram is placed in a test tube and dried at 130 ° C for 12 hours under vacuum Under the gas, after maintaining the melting at 300 ° C for 2 hours, the following formula is used to calculate the characteristic viscosity ([IV] f ) number); TS = 〇 · 245 { [IV], 1.47 - [IVV1.47} The "non-circulating nitrogen atmosphere" means that the nitrogen atmosphere does not flow. For example, the resin sheet is placed in a test tube which is connected to the vacuum line, and the nitrogen gas is depressurized and sealed for 5 times or more, and then sealed with nitrogen gas at 100 Torr to be in a sealed state. -33- 1276646 V. INSTRUCTION OF THE INVENTION (32) By using a catalyst of such a composition, it is possible to obtain a heat of fusion with respect to a molded article such as a film, a bottle, or a fiber. It is remarkably excellent, and a molded article having a reduced molecular weight, coloration, or a small amount of foreign matter occurs. Preferably, TS is below 0.77, and particularly preferably below 0.15. In the past, it has not been known that a polyester polymerization catalyst capable of imparting PET in the above range of TS. According to the present invention, not only a polyester polymerization catalyst capable of imparting PET in the above range of TS is found, but another feature of the present invention is the discovery of a film or a bottle formed by polymerizing polyester using the polyester polymerization catalyst. Hollow molded products, fiber engineering plastics, etc., can significantly improve the thermal stability during melt forming, and can be obtained even if the resin is bonded or the chips generated during molding are reused. product. The composition used as the catalyst component is preferably at least one selected from the group consisting of the above-mentioned polyester polymerization catalysts and phosphorus components. Another polyester polymerization catalyst of the present invention is a metal or metal compound and a phosphorus compound, characterized in that the activity parameter (AP) satisfies the following formula (10); (10) AP (minute) < APX (minutes); (However, AP is a polyethylene terephthalate having a polymerization characteristic viscosity of 0.65 dl / gram at a pressure of 27 5 ° C and 0.1 Toli using a predetermined amount of catalyst. Time (minutes) required for the diester (PET); APX represents the time (minutes) required to polymerize the PET under the same conditions and under the same conditions as those of the above metal or metal compound. -34- 1276646 V. INSTRUCTIONS (33) The measurement method of the AP is specifically as follows. 1) (BHET manufacturing step) using ethylene glycol twice as much as citric acid to produce bis(2-hydroxyethyl)-p- phthalate (MET) and oligomers having an esterification rate of 95%. A mixture (hereinafter, referred to as a BHET mixture). 2) (catalyst addition step) A predetermined amount of the catalyst is added to the BHET mixture, and the mixture is stirred under a nitrogen atmosphere at normal pressure at 245 ° C for 10 minutes, and then heated to 275 ° C for 50 minutes to continue the oligo. The reaction pressure of the polymixture was slowly lowered to 〇. 1 Toli. 3) (Polycondensation step) A polycondensation reaction was carried out at 275 ° C and 0.1 Torr to polymerize until the intrinsic viscosity (IV) of polyethylene terephthalate reached 0.65 dl/g. 4) The polymerization time required in the polycondensation step is AP (minutes). Here, it is carried out using a batch reactor. 1) (BHET manufacturing step) The production of the BHET mixture can be carried out by a known method. For example, two times the amount of ethylene glycol of decanoic acid is put into a batch autoclave equipped with a stirrer, pressurized at 0.25 MPa, and the water outside the system is distilled off at 245 ° C, followed by esterification. Chemical reaction manufacturing. When the activity parameter AP is within the above range, not only the thermal stability is improved by the coexistence of the phosphorus compound, but also the reaction rate becomes relatively fast, so that the production time of the polycondensation polyester is shortened. AP is preferably below 0.9 APX, more preferably below 0.8 APX, and particularly good below 0.7 APX. -35- 1276646 V. INSTRUCTIONS (34) 2) "Predetermined amount of catalyst" in the catalyst addition step means that the amount of catalyst used is changed in response to the activity of the catalyst; The amount of catalyst with low activity is high. In general, phosphorus compounds are known to be used as stabilizers for polyesters, although it is known to inhibit thermal degradation of polyesters; but it is not known that the active parameter AP is within the above range of metals, or A metal polymer and a polyester polymerization catalyst formed with a phosphorus compound. In fact, when a typical catalyst of a polyester polymerization catalyst, that is, a polymerization catalyst made of a ruthenium compound, a titanium compound, or a ruthenium compound, is added to a polymer polyester, the addition of a phosphorus compound cannot be confirmed to promote polymerization. Substantial role. According to the present invention, a polyester polymerization catalyst composed of a metal, or a metal compound, and a phosphorus compound having an activity parameter AP within the above range is found, characterized in that it is touched by the use of the polyester polymerization catalyst. The polymerization activity is excellent, and when the catalyst is deactivated or not removed, it is possible to impart a polymerization catalyst which suppresses the heat deterioration effect at the time of melt molding and obtains a polyester having excellent thermal stability. The above polyester polymerization catalyst is preferably a thermal stability parameter (TS) of polyethylene terephthalate (PET) polymerized further using the catalyst to satisfy the following formula (9): (9) TS < 0.20 By using the catalyst of such a composition, the catalyst activity is excellent, and it is possible to obtain a heat-melting property in the production of a molded article such as a film, a bottle or a fiber, and the heat stability of the melt is remarkably good, and A polyester which produces a molded article having a reduced molecular weight, coloration, and a small amount of foreign matter is imparted. -36- 1276646 V. INSTRUCTIONS (35) TS is preferably below 〇 · 18 or less; particularly good is below 0 · 15. The polyester polymerization catalyst of the present invention is preferably a thermal oxidation stability parameter (TOS) of polyethylene terephthalate (PET) polymerized using the catalyst to satisfy the following formula (11): (11) TOS < 0.10 In the above formula, TOS means a PET resin sheet having a melt polymerization IV of 0.64 to 0.66 dl/g, which is freeze-pulverized into a powder of 20 mesh or less, and 0.3 g of the film is dried under vacuum at 130 ° C for 12 hours. The test tube was placed in a test tube and dried under vacuum at 70 ° C for 12 hours. After heating at 230 ° C for 15 minutes in a dry air with silicone, the IV 値 was calculated by the following formula; TOS = 0·245 { [ IV]fi·147 - [IV], 1.47} [IV] i and [IV]fl are IV (dl/g) before and after the heating test, respectively. An example of a heating method for drying air by means of silicone rubber is, for example, a drying tube of a glued glue which is attached to the upper end of the glass test tube and heated by a dry air. By using the catalyst of the above composition, a film which imparts excellent heat aging resistance, and a molded article such as a bottle can be obtained. The TOS is preferably below 0.09; particularly preferably below 0.08. In the present invention, the PET resin sheet used for TS and TOS is measured by using the steps 1) to 3) and then quenching from a molten state. The shape of the resin sheet used herein is, for example, a resin sheet having a cylindrical shape of a length of -37 to 1276646, a description of (36) of about 3 mm and a diameter of about 2 mm. Further, the polyester polymerization catalyst of the present invention preferably has an activity parameter (AP) which satisfies the following formula (1 2 ): (12) AP (minutes) < 2T (min.) T represents an AP in the case where the ruthenium atom is 0.05 mol% based on the acid component in the polyethylene terephthalate produced by using ruthenium trioxide as a catalyst. . In the present invention, for comparison with antimony trioxide, antimony trioxide having a purity of 99% or more is used. For example, a commercially available ruthenium (ΙΠ) oxide (Adriatic Chemical Co., Ltd., purity: 99.99 9%) is used. In order to shorten the time for producing the polyester by polycondensation, it is preferred to accelerate the reaction rate by setting the activity parameter AP within the above range. Preferably, the AP is at least 1.5T, more preferably at least 1. 3T, and particularly preferably at most below 1.0T. The metal component constituting the polyester polymerization catalyst of the present invention is not particularly limited to a substance other than ruthenium, titanium, and ruthenium, but is preferably an alkali metal, an alkaline earth metal, or an aluminum. Or DIA group elements such as gallium; Group IV elements such as lanthanum; various transition metals; and lanthanides. Among them, the IE A group element is ideal, and it is more suitable for aluminum. The compound of the metal, for example, is not particularly limited, but is preferably a saturated aliphatic carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid or oxalic acid of the metal; acrylic acid, methacrylic acid, etc. An unsaturated aliphatic carboxylic acid; an aromatic carboxylic acid salt such as benzoic acid; a halogen-containing carboxylic acid such as trichloroacetic acid-38- 1276646 5. Description of the invention (37) Acid salt; hydroxyl group of lactic acid, citric acid, salicylic acid or the like Carboxylate; mineral acid salt of carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogencarbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, chloric acid, bromic acid, etc.; - an organic sulfonic acid such as propane sulfonic acid, 1-pentane sulfonic acid or naphthalene sulfonic acid; an organic sulphate such as lauryl sulphate; methoxy, ethoxy, propoxy, iso-propoxy, η-butoxy, Alkoxides such as third-butoxygen; chelating compounds such as acetamidine acetate; hydrides, oxides, hydroxides, and the like. The preferred amount of the above metal component used in the production of the polyester varies depending on the kind of the metal to be used; but it is preferably at 1 X 1 relative to the number of moles of the polycarboxylic acid unit constituting the polyester. 〇·6 or more and 0.5 mol% or less; more preferably 5 X 10·5 to 0.1 mol%. When the amount added is more than 0.5 mol%, the quality of the obtained polyester, such as heat stability and color tone, may be lowered. When the added amount is less than 1 X W6 mol%, the effect of the addition is not clear. The polyester polymerization catalyst of the present invention is preferably one which contains at least one selected from the group consisting of aluminum and a compound thereof as a constituent of a catalyst. The amount of the aluminum compound which is not aluminum in the present invention is preferably from 0.001 to 0.05 mol% based on the number of moles of all the carboxylic acid components of the dicarboxylic acid and the polycarboxylic acid in the polyester; More preferably 0.005 to 0.02% by mole. When the amount used is less than 0.001 mol%, the activity of the catalyst will not be sufficiently exerted; when the amount used exceeds 0.05 mol%, the thermal stability and the thermal oxidation stability are lowered. There is a problem that the foreign matter caused by aluminum causes an increase in coloration. The addition of such a small amount of aluminum component - 39 - 1276646 5 , the invention description (38), is also a significant feature of the polymerization catalyst of the present invention which exhibits sufficient catalytic activity characteristics. As a result, the thermal stability and thermal oxidation stability obtained are excellent, and the foreign matter and coloring caused by aluminum are lowered. The amount of the phosphorus compound used in the present invention is preferably from 0.0001 to 0.1 mol%, more preferably from 0.005 to 0.05 mol, based on the number of moles of all constituent units of the polycarboxylic acid component in the polyester. %. When the amount of the phosphorus compound added is less than 0.0001% by mole, the effect of the addition is not clear; when the amount of the phosphorus compound added exceeds 0.1% by mole, the opposite activity of the catalyst as the polyester decline. The technique of using a catalyst component mainly composed of an aluminum compound without using a phosphorus compound is to reduce the amount of the aluminum compound used, and further reduce the thermal stability by adding an aluminum compound as a catalyst to the cobalt compound. While the technique of preventing coloration is added, when the cobalt compound is added to a level sufficient for catalytic activity, the thermal stability is lowered. Therefore, this technology has the difficulty of both. According to the present invention, it is possible to use a specific amount of a phosphorus compound without causing problems such as a decrease in thermal stability and generation of foreign matter, but it is possible to obtain a small amount of aluminum in a metal-containing component, but has sufficient contact. By using such a polymerization catalyst, it is possible to improve the thermal stability of a hollow molded article such as a polyester film or a bottle, a fiber, or an engineering plastic at the time of melt molding. In the phosphorus compound of the present invention, it is not preferable to add an effect of adding phosphoric acid ester such as phosphoric acid or trimethylphosphoric acid to enhance the catalytic activity. Further, the amount of the phosphorus compound of the present invention to be added in the present invention is in the range of -40 to 1276646. 5. The invention (39) may be used in combination with a compound containing a ruthenium compound, a titanium compound or a ruthenium compound, but it is not possible. The effect of promoting the melt polymerization reaction was confirmed. The constituent component of the polyester polymerization catalyst of the present invention is preferably at least one selected from the group consisting of aluminum salts containing a phosphorus compound. It may be used in combination with an aluminum compound other than the salt of the phosphorus compound or a phosphorus compound. The amount of the aluminum salt of the phosphorus compound in the present invention is preferably from 0.0001 to 0-2 mol%, more preferably 0.005 to 0.1 mol, based on the number of moles of all constituent units of the polycarboxylic acid component in the polyester. ear%. Further, another feature of the present invention is that the aluminum carboxylate salt previously dissolved in water and/or an organic solvent is used as a catalyst. As the aluminum carboxylate salt of the present invention, for example, specifically, for example, aluminum formate, aluminum acetate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, Aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum sulphate, aluminum tartrate, aluminum sulphate, etc.; but in terms of solubility and activity of the catalyst, it is preferred to have aluminum acetate, base aluminum acetate An aluminum acetate salt structure or an aluminum lactate system. The aluminum salt of a carboxylic acid is used as an example of a polyester polymerization catalyst, and examples thereof include aluminum acetate, aluminum acetate base, aluminum lactate, aluminum benzoate, etc., but since any of them is for polyester Since the solubility is low and the catalytic activity is also poor, there is a problem that foreign matter which is insoluble to the obtained polyester is generated, and there is a problem in using these compounds as a catalyst. According to the present invention, the use of a substance previously dissolved in water and/or an organic solvent as a catalyst will reveal a significant feature of possessing sufficient catalytic activity characteristics. -41 - 1276646 V. INSTRUCTION OF THE INVENTION (4〇) The aluminum carboxylate salt of the present invention is required to be dissolved in water and/or an organic solvent before being added to the polymerization system of the polyester, and then added to Polymerization system. For use as an organic solvent, it is preferably a glycol; in the case of PET, it is preferred to use ethylene glycol. As a structure having an aluminum salt of acetic acid, for example, a base of aluminum acetate, aluminum triacetate, an aluminum acetate solution or the like; wherein, depending on solubility and stability of the solution, it is preferred to use Base aluminum acetate. It is necessary to dissolve any of the base aluminum acetate in water and/or an organic solvent to use it as a catalyst. By using a catalyst having such a composition, a polyester having excellent catalyst activity and excellent quality can be obtained. As a solvent, it is preferred to use water or glycols; in the case of PET, it is preferred to use water or ethylene glycol. Further, according to the present invention, when an aluminum carboxylate salt stabilized by boric acid or the like is used as a catalyst, it is found that both solubility and stability of the solution are excellent, and the catalytic activity is excellent and the quality is excellent. A major feature of polyester. It can be used as an aluminum salt of a carboxylic acid, preferably a structure having an aluminum salt of acetic acid; and it is preferred to use a base aluminum acetate. As the stabilizer, for example, urea, thiourea or the like is used in addition to boric acid, but boric acid is preferably used. In the case of using boric acid to stabilize, it is preferred to use a boric acid having a molar amount of less than or equal to the amount of aluminum to be stabilized. In this case, it is preferred to use a boric acid of 1 / 2 to 1 / 3 molar amount to stabilize the boric acid. Aluminum compound. From the viewpoint of catalyst activity and quality of the polyester, it is preferred to add a dissolved polymerization system which is previously dissolved in water and/or an organic solvent. As the organic solvent, it is preferred to use -42- 1276646, the invention (41) diols; in the case of PET, it is preferred to use ethylene glycol. In WO 98/42769, it is disclosed that a mixture of a base aluminum acetate and a basic compound such as tetraethylamine hydroxide is used as a catalyst. This method describes a method for suppressing the formation of insoluble foreign matter. However, according to this technique, it is necessary to use a basic compound; therefore, there is a problem that the alkali compound causes coloring or foreign matter of the polyester. According to the present invention, the basic compound described in the patent does not need to be previously mixed with the aluminum compound of the present invention, so that the polyester phthalate which reduces the above-mentioned coloring and foreign matter problem can be obtained by dissolving the aluminum carboxylate in advance in order to manufacture the present invention. The solution in water and/or an organic solvent is preferably a solution in which aluminum carboxylate is dissolved in water. In the aqueous solution, it is preferred to add an organic solvent such as a glycol as appropriate. The aqueous solution may be added to the original polymerization system. For the purpose of thermal shock reduction, it is preferred to add a solution obtained by diluting the solution with a glycol such as ethylene glycol to the polymerization system, or to add a solution diluted with a glycol. The liquid is replaced by a liquid-liquid and the water is distilled off into the polymerization system. In the case where the solution is diluted with a diol such as ethylene glycol, it is preferably diluted with a diol having a volume ratio of 0.5 to 50 times relative to the volume ratio of water. Further, in order to make it difficult to form an insoluble foreign matter in the obtained polyester and suppress it, the concentration of the aluminum carboxylate solution added to the polymerization system is preferably 0.01 to 1 mol/liter in terms of aluminum atom. . When the aluminum carboxylate salt is dissolved in water and/or an organic solvent, or a boric acid or the like is added to the dissolved solution, or a citric acid-43- 1276646 5. Description of the invention (42) Acids such as lactic acid and oxalic acid are preferred because they improve solubility and stability of the solution. The following is a specific example of a method of preparing a solution by dissolving the base aluminum acetate used in the present invention in water and/or an organic solvent. <Preparation example of aqueous solution of base aluminum acetate> The base aluminum acetate was added to water and stirred at room temperature for several hours or more. The stirring time is preferably more than 12 hours. Thereafter, the mixture was stirred at 60 ° C or higher for several hours. The temperature in this case is preferably in the range of 60 to 80 °C. The stirring time is preferably more than 3 hours. The concentration of the aqueous solution is preferably from 5 g/l to 100 g/l; more preferably from 10 g/l to 30 g/l. <Preparation example of base ethylene glycol solution of ethylene glycol> The opposite ethylene glycol was added to the above aqueous solution. The amount of ethylene glycol added is preferably from 1 to 5 times the volume ratio of the aqueous solution. More preferably 2 to 3 times the amount. The solution was stirred at room temperature for several hours to obtain a uniform water/glycol mixed solution. Thereafter, the solution was heated, and water was distilled off to obtain an ethylene glycol solution. The temperature is preferably above 80 ° C and below 120 ° C. It is more preferred to stir at 90 to 110 ° C for several hours to distill off water. The following examples are specific examples of a method for preparing an aluminum glycol solution of aluminum lactate used in the present invention. Aqueous solution of aluminum lactate is prepared. The modulation system can be carried out at room temperature or under heating, preferably at room temperature. The concentration of the aqueous solution is preferably 20 g/l to i 00 g/l; more preferably 50 g/l to 80 g/l. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added, relative to the volume ratio of the aqueous solution, is -44 to 1276646. 5. The invention (43) is preferably 1 to 5 times the amount. More preferably 2 to 3 times the amount. After the solution was stirred at normal temperature to obtain a uniform water/ethylene glycol mixed solution, the solution was heated, and water was distilled off to obtain an ethylene glycol solution. The temperature is preferably above 80 ° C and below 120 ° C. More preferably, it is mixed at 90 to 110 ° C for several hours to distill off water. The aluminum carboxylate salt having the polyester polymerization catalyst of the present invention is dissolved in a solution of water and/or an organic solvent, preferably at least one selected from the group consisting of phosphorus compounds, so that the solution The stability is increased and the formation of foreign matter is suppressed. When the aluminum carboxylate salt is dissolved in water and/or an organic solvent to prepare a solution, it may coexist with at least one selected from the group consisting of phosphorus compounds. The amount of the phosphorus compound added is preferably in the range of 0.1 to 10 with respect to the molar ratio of the phosphorus atom of the aluminum atom. In the method of adding the phosphorus compound, the phosphorus compound may be added to the previously prepared aluminum compound solution, and the aluminum compound may be dissolved in the previously prepared phosphor compound solution. Alternatively, the two solutions may be mixed and prepared, or both may be dissolved in a solvent at the same time. As a solvent, it is preferred to use water or a glycol; in the case of PET, it is preferred to use water and/or ethylene glycol. When the polyester is produced by the method of the present invention, the aluminum atom is preferably 0.01 to 0.05 mol%, based on the number of moles of all the constituent units of the carboxylic acid component such as the dicarboxylic acid and the polycarboxylic acid in the polyester. It should be 0.005~0.02 mol%. When the amount used is less than 0 · 00 1 mol%, the catalyst activity is difficult to fully exert; when the amount used is more than 〇.〇5 mol%, thermal stability -45-1276646 V. Description of the invention (44) Or the thermal oxidation stability may be lowered, and a problem arises in that the aluminum compound is insoluble to the polyester, or the coloring is increased. The addition of such a small amount of aluminum component is also a significant feature of the polymerization catalyst of the present invention which exhibits sufficient catalytic activity characteristics. As a result, the thermal stability and thermal oxidation stability obtained were excellent, and the foreign matter and coloring caused by aluminum were lowered. According to the method of the present invention, when at least one selected from the group consisting of phosphorus compounds is used in the production of the polyester, the effect of improving physical properties such as thermal stability of the polymer can be found.摩尔%。 The amount of the aluminum atom is preferably 0.0001~0. 1 mol%, based on the number of moles of the constituent units of the polycarboxylic acid in the polyester. More preferably, it is 0.005~0.05 mol%. In the case of using a catalyst prepared by adding a phosphorus compound to the aluminum carboxylate having the polyester polymerization catalyst of the present invention, the amount of the catalyst added is preferably such that the amount of the phosphorus compound added is within the above range. . When the catalyst solution other than the phosphorus compound is added, the total amount of the phosphorus compound to be added to the polymerization system is preferably within the above range. By using the phosphorus compound of the present invention for use, it is possible to obtain a catalyst which sufficiently exhibits a catalytic effect in a polyester polymerization catalyst with a small amount of added aluminum. When the amount of the phosphorus compound added is less than 〇·莫1 mol%, it is difficult to sufficiently exhibit the effect of adding a catalyst; and when the amount added exceeds 〇1 mol%, the opposite is In the case where the catalytic activity is lowered, the tendency to decrease varies depending on the amount of use of aluminum or the like. In the case of producing a polyester according to the method of the present invention, it is preferred to not add -46 - 1276646. 5. Description of the invention (45) An alkali metal, an alkaline earth metal or a compound thereof. Further, in one aspect, a preferred embodiment of the present invention is to add at least one selected from the group consisting of a small amount of an alkali metal, an alkaline earth metal, and a compound thereof added to aluminum and a compound thereof. 2 metal components. Further, in the specific embodiment of the polyester polymerization catalyst of the present invention, it is preferred to coexist with the second metal-containing component. Further, at the time of the polymerization, at least one selected from the group consisting of alkali metals, alkaline earth metals, and compounds thereof may be added to the solution of the polyester polymerization catalyst of the present invention, and may be added to the alkali metal or alkaline earth. At least one selected from the group consisting of metals and their compounds may be used in other catalyst solutions. When such a second metal-containing component is added, in addition to the effect of suppressing the formation of diethylene glycol, high catalytic activity can be obtained, and a catalyst component having a relatively high reaction rate can be obtained, and productivity can be effectively improved. . The addition of an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalytically active catalyst is a well-known technique. When such a known catalyst is used, although a polyester excellent in thermal stability can be obtained, a known catalyst for use with an alkali metal compound or an alkaline earth metal compound needs to be added more than a practical catalyst activity. The amount of foreign matter due to the use of alkali metal will increase; the silkiness or silk property used on the fiber, or the film property, transparency, thermal stability, thermal oxidation stability, and resistance when used on a film Hydrodecomposition and the like are all deteriorated. Further, the color tone of the melt-molded article such as a fiber or a film is also deteriorated. Further, in the case of using an alkaline earth metal compound, in order to obtain practical activity, the obtained polyester-47-I276646 5, the invention (46) & thermal stability and thermal oxidation stability are all lowered. The color will increase due to heating, and the amount of foreign matter will increase. In the case where an alkali metal, an alkaline earth metal, and a compound thereof are added, it is used in centistokes (mol%), and its content is preferably from 1 X 1 with respect to the number of moles of all the polybasic decanoic units constituting the polyester. 0 · 6 or more to less than 0 · 1 mol %; more preferably 5xl 〇 6~0.05 mol%; more preferably 1 ΧΙΟ.5~〇.〇3 莫%; particularly suitable is from 1 X 10 · 5 ~ 0.01 mol%. When the content of the alkali metal or the alkaline earth metal is small, the thermal stability is deteriorated, the hydrodegradability is lowered, and foreign matter or coloration is caused. When the amount of the alkali metal, the alkaline earth metal, and the compound used is 0.1 mol% or more, the thermal stability is deteriorated, foreign matter is increased, coloring is increased, and hydrogenation resistance is lowered. When the tether is less than 1 X 1 〇·6 mol%, the effect of inclusion is not clear. In the case of producing a polyester according to the method of the present invention, a preferred embodiment is a further addition of a compound having a cobalt atom of less than 10 ppm with respect to the polyester. It is preferably below 5 ppm, and more preferably below 3 ppm. Further, a polymer containing a cobalt compound may be added to the polyester polymerization catalyst of the present invention at the time of polymerization, and a cobalt compound may be additionally added to the catalyst solution. Further, on the one hand, when the polyester is produced by the method of the present invention, it is preferred not to use a cobalt compound. When a polyester is produced according to the method of the present invention, a component of another polymerization catalyst such as a ruthenium compound, a titanium compound, a ruthenium compound or a tin compound is added -48-1276646. 5. Description of the invention (47), the coexistence of the addition is used. The amount is preferably such that it does not cause the above problems in the properties of the polyester, the processability, the color tone, and the like, and it is advantageous in shortening the polymerization time and improving the productivity. However, the amount of the ruthenium compound to be added is preferably 50 ppm or less based on the polyester obtained by polymerization, and more preferably 30 ppm or less. When the addition amount of the chain is more than 50 ppm, the precipitation of the metal ruthenium is caused, and the polyester is blackened and foreign matter is generated, which is not preferable. The amount of the titanium compound to be added is preferably in the range of 10 ppm or less based on the amount of the polyester obtained by polymerization. It is preferably below 5 ppm, more preferably below 2 ppm. When the added content of titanium is more than 10 ppm, the thermal stability of the obtained resin is remarkably lowered. The amount of the ruthenium compound to be added is preferably 20 ppm or less based on the polyester on the side obtained by polymerization, and more preferably 10 ppm or less. When the amount of rhodium added is more than 20 ppm, it is not suitable because it is not conducive to cost. When the polyester is produced by the method of the present invention, one type or two or more types of a ruthenium compound, a titanium compound, a ruthenium compound, and a tin compound can be used. The alkali metal and the compound thereof, and the alkaline earth metal and the compound thereof may be used as the substance of the present invention, and are not particularly limited to a certain substance. For example, for example, formic acid, acetic acid, propionic acid, butyric acid, a saturated aliphatic carboxylic acid such as oxalic acid; an unsaturated aliphatic carboxylic acid such as acrylic acid or methacrylic acid; an aromatic carboxylic acid salt such as benzoic acid; a halogenated carboxylate such as trichloroacetic acid; and milk-49-1276646 DESCRIPTION OF THE INVENTION (48) Hydroxycarboxylic acid salt of acid, citric acid, salicylic acid, etc.; carbonic acid, phosphoric acid, nitric acid, sulfuric acid, phosphonic acid, hydrogencarbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, bromination a mineral acid salt such as hydrogen acid, chloric acid or bromic acid; an organic sulfonic acid such as 1-propanesulfonic acid, 1-pentanesulfonic acid or naphthalenesulfonic acid; an organic sulfate such as lauryl sulfate; methoxy and ethoxylated An alkoxide such as η-propoxy, iso-propoxy, n-butoxy or tert-butoxy; a chelating compound such as acetamidine acetate; a hydride, an oxide, a hydroxide or the like. When a strong base such as a hydroxide is used in such a compound, since it has a tendency to be easily dissolved in an organic solvent such as glycol or ethanol such as ethylene glycol, it has to be added to the polymerization solution as an aqueous solution. The problem with the aggregation process. Further, in the case of using a strong basic substance such as a hydroxide, the polyester at the time of polymerization is susceptible to side reactions such as hydrogenation decomposition, so that the polymerized polyester has a tendency to be easily colored, so that hydrogenation resistance is resistant. Has a tendency to decrease. Therefore, it is suitable as the alkali metal of the present invention and its compound, and alkaline earth metal and its compound, for example, a saturated aliphatic carboxylic acid of the metal; an unsaturated aliphatic carboxylic acid, an aromatic carboxylate, and a halogen-containing Inorganic acid selected from the group consisting of carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, chloric acid, bromic acid, etc. Salt; organic phosphonates, organic sulfates, chelating compounds, oxides, and the like. Further, among these, an organic carboxylate, particularly an acetate, is preferred from the viewpoint of easy availability, ease of handling, and the like. The aluminum and the compound thereof may be used as the material of the present invention, and are not particularly limited to the ones described in the specification of the invention, but in addition to the metal aluminum, for example, aluminum formate may also be used. Aluminum acetate, base aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum tartrate, aluminum citrate, aluminum ruthenate, etc. Carboxylate; inorganic acid salt of aluminum chloride, aluminum hydroxide, aluminum chloride hydroxide, polyaluminum chloride, aluminum nitrate, aluminum phosphate, aluminum carbonate, aluminum phosphate, aluminum phosphonate, etc.; aluminum methoxide, Aluminum ethoxide, aluminum η-propoxide, aluminum isopropoxide, aluminum η-butoxide, aluminum t-butoxide, etc.; aluminum acetoacetate, aluminum ethyl acetonitrile acetate An aluminum bismuth compound such as aluminum ethyl acetoacetate or aluminum ethyl acetoacetate diiso-propoxide; an organoaluminum such as trimethyl aluminum or triethyl aluminum or a partially hydrogenated decomposition product thereof; a reaction product derived from an alkoxide of aluminum or an aluminum ruthenium compound and a hydroxycarboxylic acid; oxygen Aluminum, ultra-fine particles of alumina, aluminum silicate, titanium or aluminum, and silicon, or a pin or an alkali metal or alkaline earth metal, the composite oxide. Among them, carboxylate, inorganic acid salt and chelating compound are preferably used; more preferably, it is a base of aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide, and aluminum acetate.醯 salt. More preferably, it is stabilized by using an additive such as aluminum acetate. The phosphorus compound of the present invention is not particularly limited, and is, for example, a phosphate ester of phosphoric acid such as trimethylphosphoric acid, triethylphosphoric acid, phenylphosphoric acid or triphenylphosphoric acid; Such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylbenzene) phosphite, tetra (2,4-di- Tris-butylbenzene) phosphite of phosphorous acid such as 4,4'-diphenylene diphosphite. -51 - 1276646 V. DESCRIPTION OF THE INVENTION (5〇) The preferred phosphorus compound of the present invention is preferably a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, or a trivalent phosphine. At least one phosphorus compound selected from the group consisting of an acid compound and a phosphine compound. By including such a phosphorus compound, the effect of improving the physical properties of the target polyester of the present invention is improved, and when such a phosphorus compound and the aluminum compound of the present invention are coexisted in the polymerized polyester, an effect of increasing the catalytic activity can be found. Among these, when a phosphonic acid-based compound is used, the effect of increasing the activity of the catalyst is increased, which is preferable. Among the above phosphorus compounds, when a compound having an aromatic ring structure is used, the effect of improving physical properties and catalytic activity is increased, which is preferable. When the polyester of the present invention is produced, by using such a phosphorus compound, it is possible to obtain a catalyst which makes the amount of addition of the alkali metal compound or the alkaline earth metal compound small, and which fully exerts the catalytic effect. The phosphonic acid-based compound, the phosphinic acid-based compound, the phosphine oxide-based compound, the phosphinic acid-based compound, the trivalent phosphonic acid-based compound, and the phosphine-based compound have the following formulas ((1) to ((1)) For the compound of the structure represented by 6)). -52- 1276646 V. INSTRUCTIONS (51) i <tn 〇t II II 〇 P P - 〇 . I. I [Chemical 2] 〇 II II A P - 〇 "II [Chemical. 3] 〇 II II A F - I [: 4] - 〇 P —〇一 I , [Chemical 5] —P — I I I [Chem. 6] A PI -53- 1276646 V. Description of the invention (52) It can be used as the phosphonic acid compound of the present invention, for example, for example Dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, benzyl Diethyl phosphonate, etc. may be used as the phosphinic acid compound of the present invention, for example, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate. And phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, etc., which may be used as the phosphine oxide compound of the present invention, for example, diphenylphosphine oxide, for example a bisphosphonium oxide, a triphenylphosphine oxide, etc. The phosphorus of the present invention in a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, a trivalent phosphonic acid compound, or a phosphine compound Compound The compound is preferably a compound represented by the following formula ((Chem. 7) to (Chem. 12)). [Chemical 7] 〇 4η OH [Chemical 8]
-54- 1276646 五、發明說明（53) [化9]-54- 1276646 V. Description of invention (53) [Chem. 9]
[化 1 1][Chem. 1 1]
[:化 1 2] C (CHa )· (CH2 ) t ] a P 在上述磷化合物中，使用具有芳香環構造之化合物時， 可使改善物性與觸媒活性之效果變大，因而較適宜。 -55- 1276646 五、發明說明（54) 又，本發明之磷化合物當使用以下述各式（（化1 3 )〜（化 1 5 ))所代表之化合物，由於可使改善物性與觸媒活性之效 果變大，因而特別地適宜。 [化 13] P (=0)' R1 (OR2 ) (OR3 [化 1 4] P (=0) R1 R4 (OR2 ) [:化 1 5] P (=0) R1 R5 R6 (在式（化13)〜（化15)中，R1、R4、R5、R6係各自獨立 代表氫、碳數爲1〜50之烴基、含有羥基或鹵素基或烷氧 基或胺基之碳數爲1〜50之烴基。R2、R3係各自獨立代表 氫、碳數爲1〜50之烴基、含有羥基或烷氧基之碳數爲 1〜50之烴基。但是，烴基也可以含有環己基等之脂環構造 、或苯基或萘基等之芳香環構造。） 做爲本發明之磷化合物者，上述式（化1 3 )〜（化1 5 )中 ，R1、R4、R5、R6較宜是具有芳香環構造之化合物。 可做爲本發明之磷化合物者，舉例來說，例如是甲基膦 酸二甲酯、甲基膦酸二苯酯、苯基膦酸二甲酯、苯基膦酸 二乙酯、苯基膦酸二苯酯、爷基膦酸二甲酯、苄基膦酸二 -56- 1276646 五、發明說明（55) 乙酯、二苯基次膦酸、二苯基次膦酸甲酯、二苯基次膦酸 苯酯、苯基次膦酸、苯基次膦酸苯酯、二苯基膦氧化物、 甲基二苯基膦氧化物、三苯基膦氧化物等。其中較宜是苯 基膦酸二甲酯、苄基膦酸二乙酯。 上述磷化合物中，依照本發明而言，特別合宜的是p化 合物與磷之金屬鹽化合物。磷之金屬鹽化合物’若是磷化 合物之金屬鹽雖然並沒有特別地限定，但是使用膦酸系化 合物之金屬鹽，由於可改善本發明目標之聚酯的物性與觸 媒活性之效果會變大，因而較適宜。磷化合物之金屬鹽’ 較宜是含有單一金屬鹽、二金屬鹽、三金屬鹽等。 又，上述之磷化合物中金屬鹽的金屬部分，當使用Li、 Na、K、Be、Mg、Sr、Ba、Μη、Ni、Cu、Zn 等選出之物時 ，提高觸媒活性之效果會變大，因而較適宜。其中，較宜 是 Li、Na、Mg 〇 本發明之磷化合物當使用以下述各式（化1 6 )所代表之化 合物中選取之至少一種時，由於可使改善物性與觸媒活性 之效果變大，因而較適宜。 [化 1 6 ] / 〇 \ R1~(CH2)n-P—〇' ) M (R3〇-)m 、 OR2 Λ (在式（化16)中，R1係代表氫、碳數爲卜“之烴基、含 -57- 1276646 五、發明說明（56 ) 有羥基或鹵素基或烷氧基或胺基之碳數爲1〜5〇之烴基。 R2係代表氫、碳數爲1〜50之烴基、含有羥基或烷氧基之 碳數爲1〜50之烴基。R3係代表氫、碳數爲1〜50之烴基、 含有羥基或烷氧基或羰基之碳數爲1〜50之烴基。1係代表 1以上之整數；m爲代表0或1以上之整數；1 +m係在4以 下。Μ係代表（1+m)價之金屬陽離子。n係代表1以上之整 數。烴基也可以含有環己基等之脂環構造或分枝構造或苯 基或萘基等之芳香環構造。） 可做爲上述R1者，舉例來說，例如是苯基、1 -萘基、2-萘基、9-蒽基、4-聯苯基、2-聯苯基等。可做爲上述R2者 ，舉例來說，例如是氫、甲基、乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基、長鏈之脂肪族基、苯基、萘 基、經取代之苯基或萘基、以CH2CH2OH所代表之基。可做 爲R30_者，舉例來說，例如是氫氧化物離子、烷酯離子、 乙酸鹽離子、或乙醯酮離子等。 在上述以式（化1 6 )所代表之化合物中，也較宜是使用自 以下述通式（化1 7 )所代表之化合物中選取之至少一種。 [化 17] 0 R1—CH2—P—〇-〇C2H5 (在式（化17)中，R1係代表氫、碳數爲1〜50之烴基、含When a compound having an aromatic ring structure is used as the phosphorus compound, the effect of improving physical properties and catalytic activity can be increased, which is preferable. -55- 1276646 V. Inventive Note (54) Further, the phosphorus compound of the present invention can improve the physical properties and the catalyst by using a compound represented by the following formula ((Chem. 13) to (Chem. 15)). The effect of the activity becomes large, and thus it is particularly suitable. P (=0)' R1 (OR2 ) (OR3 [Chemical 1 4] P (=0) R1 R4 (OR2 ) [:1 1] P (=0) R1 R5 R6 (in the formula 13) In the formula (1), R1, R4, R5 and R6 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group or an alkoxy group or an amine group, and the carbon number is 1 to 50. The hydrocarbon group. R2 and R3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. However, the hydrocarbon group may also contain an alicyclic structure such as a cyclohexyl group. Or an aromatic ring structure such as a phenyl group or a naphthyl group.) In the case of the phosphorus compound of the present invention, in the above formula (Chemical Formula 1) to (Chemical Formula 1), R1, R4, R5, and R6 are preferably aromatic. A compound of a ring structure. It can be used as a phosphorus compound of the present invention, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, phenylphosphonic acid Ethyl ester, diphenyl phenylphosphonate, dimethyl arylphosphonate, benzylphosphonic acid bis-56-1276646 V. Description of the invention (55) Ethyl ester, diphenylphosphinic acid, diphenylphosphinium Methyl ester, phenyl diphenylphosphinate, phenylphosphinic acid Phenyl phenylphosphinate, diphenylphosphine oxide, methyl diphenylphosphine oxide, triphenylphosphine oxide, etc. Among them, dimethyl phenylphosphonate and diethyl benzylphosphonate are preferred. Among the above-mentioned phosphorus compounds, a metal compound of a p compound and a phosphorus compound is particularly preferable according to the present invention. The metal salt of a phosphorus compound, if not a metal salt of a phosphorus compound, is not particularly limited, but a phosphonic acid system is used. The metal salt of the compound is suitable because the effect of improving the physical properties and the catalytic activity of the polyester of the present invention is relatively large. The metal salt of the phosphorus compound is preferably a single metal salt, a two metal salt or a trimetallic metal. Further, when the metal portion of the metal salt in the above phosphorus compound is selected from Li, Na, K, Be, Mg, Sr, Ba, Μη, Ni, Cu, Zn, etc., the catalytic activity is improved. The effect is increased, and it is more preferable. Among them, Li, Na, and Mg are preferable. When the phosphorus compound of the present invention is at least one selected from the compounds represented by the following formulas (Chem. 16), Improve physical properties and catalytic activity The effect is larger and thus more suitable. [Chemical 1 6 ] / 〇\ R1~(CH2)nP-〇' ) M (R3〇-)m , OR2 Λ (In the formula (Chem. 16), R1 represents hydrogen The hydrocarbon number of the carbon number is "57- 1276646", and the invention has (56) a hydrocarbon group having a hydroxyl group or a halogen group or an alkoxy group or an amine group having a carbon number of 1 to 5 Å. R2 represents hydrogen and carbon. a hydrocarbon group having 1 to 50, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms, and R 3 representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a carbon group having a hydroxyl group or an alkoxy group or a carbonyl group; a hydrocarbon group of 1 to 50. The 1 series represents an integer of 1 or more; m is an integer representing 0 or more; 1 + m is 4 or less. The lanthanide represents a metal cation of (1+m) valence. The n system represents an integer of 1 or more. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. As the above R1, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 4-biphenyl group, a 2-biphenyl group or the like can be mentioned. As the above R2, for example, hydrogen, methyl, ethyl, propyl, isopropyl, η-butyl, t-butyl, tert-butyl, long-chain aliphatic groups, Phenyl, naphthyl, substituted phenyl or naphthyl, represented by CH2CH2OH. It may be, for example, R30_, such as a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion. In the compound represented by the above formula (Chem. 16), it is also preferred to use at least one selected from the compounds represented by the following formula (Chemical Formula 7). 0 R1—CH 2 —P—〇—〇 C 2 H 5 (In the formula (Chem. 17), R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and
M (RsCT)r -58- 1276646 五、發明說明（57) 有羥基或鹵素基或烷氧基或胺基之碳數爲1〜50之烴基。 R3係代表氫、碳數爲1〜50之烴基、含有羥基或烷氧基或 羰基之碳數爲1〜50之烴基。1係代表1以上之整數；m爲 代表0或1以上之整數；1+m係在4以下。Μ係代表（1+m) 價之金屬陽離子。烴基也可以含有環己基等之脂環構造或 分枝構造或苯基或萘基等之芳香環構造。） 可做爲上述R1者，舉例來說，例如是苯基、1-萘基、2-萘基、9-蒽基、4-聯苯基、2-聯苯基等。可做爲R3(T者， 舉例來說，例如是氫氧化物離子、烷酯離子、乙酸鹽離子 、或乙醯酮離子等。 上述之磷化合物中，當使用具有芳香族構造之化合物時 ，可使改善物性與觸媒活性之效果變大，因而較適宜。 在上述式（化17)中，當Μ係使用自Li、Na、K、Be、Mg 、Sr、Ba、Μη、Ni、Cu、Zn等中選取之物時，由於可使改 善物性與觸媒活性之效果變大，因而較適宜。其中，更宜 是 Li 、 Na 、 Mg 〇 用來做爲本發明之磷的金屬鹽化合物者，舉例來說，例 如是[(卜萘基）甲基膦酸乙基]鋰、[(1-萘基）甲基膦酸乙 基]鈉、二[(1-萘基）甲基膦酸乙基]鎂、[(2 -萘基）甲基膦 酸乙基]鉀、二[(2-萘基）甲基膦酸乙基]鎂、[苄基膦酸乙 基]鋰、[苄基膦酸乙基]鈉、二[苄基膦酸乙基]鎂、二[苄 基膦酸乙基]皴、二[苄基膦酸乙基]緦、二[苄基膦酸乙基] 錳、苄基膦酸鈉、二[苄基膦酸]鎂、[(9-蒽基）甲基膦酸 -59- 1276646 五、發明說明（58) 乙基]鈉、二[(9-蒽基）甲基膦酸乙基]鎂、[4-羥基苄基膦 酸乙基]鈉、二[4-羥基苄基膦酸乙基]鎂、[4-氯化苄基膦 酸苯基]鈉、二[4-氯化苄基膦酸乙基]鎂、[4-胺基苄基膦 酸甲基]鈉、二[4-胺基苄基膦酸甲基]鎂、苯基膦酸鈉、 二[苯基膦酸乙基]鎂、二[苯基膦酸乙基]鋅等。其中，較 宜是[(1 -萘基）甲基膦酸乙基]鋰、[(1 -萘基）甲基膦酸乙 基]鈉、二[(1-萘基）甲基膦酸乙基]鎂、[苄基膦酸乙基] 鋰、[苄基膦酸乙基]鈉、二[苄基膦酸乙基]鎂、苯基膦酸 鈉、二[苯基膦酸]鎂。 在上述之磷化合物中，就本發明來說，較宜是與具有至 少一個P-OH鍵之磷來做爲磷化合物。利用含有此種磷化 合物時，除了發現使得本發明目標聚酯物性的改善效果變 高，尙且發現於聚酯之聚合時，本發明之鋁化合物與該種 磷化合物共存使用下，可使觸媒活性之提昇效果變大。 具有至少一個P-OH鍵之磷化合物，並並沒有特別地限 定爲在分子內具有至少一個P-OH鍵之磷化合物。在此等 磷化合物之中，當使用具有至少一個P-OH鍵之磷化合物 時，可使改善聚酯之物性與觸媒活性之提昇效果變大，因 而較適宜。 在上述磷化合物中，使用具有芳香環構造之化合物時， 可使改善物性與觸媒活性之提昇效果變大，因而也適宜。 又，本發明之具有至少一個P-OH鍵之磷化合物，當使 用以下述通式（化1 8 )所代表之化合物，由於可使改善物性 -60- 1276646 五、發明說明（59) 與觸媒活性之提昇效果變大，因而較適宜。 [化 18]0 R1—(CH2)n - 〒 一 〇HOR2 (在式（化18)中，R1係代表氫、碳數爲1〜50之烴基、含 有羥基或鹵素基或烷氧基或胺基之碳數爲1~50之烴基。 R2係代表氫、碳數爲1〜50之烴基、含有羥基或烷氧基之 碳數爲1〜50之烴基。η係代表1以上之整數。烴基也可以 含有環已基等之脂環構造或分枝構造或苯基或萘基等之芳 香環構造。） 可做爲上述R1者，舉例來說，例如是苯基、1-萘基、2-萘基、9-蒽基、4-聯苯基、2-聯苯基等。可做爲上述R2者 ’舉例來說，例如是氫、甲基、乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基、長鏈之脂肪族基、苯基、萘 基、經取代之苯基或萘基、以CH2CH20H所代表之基。 在上述磷化合物中，使用具有芳香環構造之化合物時， 可使改善物性與觸媒活性之提昇效果變大，因而也適宜。 可做爲本發明之具有至少一個P-0H鍵之磷化合物者， 舉例來說，例如是（1-萘基）甲基膦酸乙酯、（1-萘基）甲基 膦酸、（2-萘基）甲基膦酸乙酯、苄基膦酸乙酯、苄基膦酸 、（9-蒽基）甲基膦酸乙酯、4-羥苄基膦酸乙酯、2-甲苄基 膦酸乙酯、4-氯化苄基膦酸苯酯、4-胺苄基膦酸甲酯、4- -61 - 1276646 五、發明說明（60) 甲氧苄基膦酸乙酯等。其中，較宜是（1-萘基）甲基膦酸乙 酯、苄基膦酸乙酯等。 可做爲本發明較佳之磷化合物者，舉例來說’例如是以 化學式（化19)所代表之化合物等。 [化 19] R1 — CH2 — P (=〇） (OR2 ) (OR3 ) (在式（化19)中，R1係代表氫、碳數爲1〜49之烴基、含 有羥基或鹵素基或烷氧基或胺基之碳數爲1〜49之烴基。 R2、R3係各自獨立地代表氫、碳數爲1〜50之烴基、含有 羥基或烷氧基之碳數爲1〜50之烴基。烴基也可以是含有 環己基等之脂環構造或分枝構造或苯基或萘基等之芳香環 構造。） 又，更宜是R1、R2、R3中至少含有一個芳香環構造之化 合物。 此種磷化合物之具體實施例，係如以下所示。 [化 2 0]M (RsCT) r -58-1276646 V. Description of the invention (57) A hydrocarbon group having a hydroxyl group or a halogen group or an alkoxy group or an amine group having a carbon number of 1 to 50. R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or alkoxy group or a carbonyl group and having 1 to 50 carbon atoms. The 1 series represents an integer of 1 or more; m is an integer representing 0 or more; 1 + m is 4 or less. The lanthanide represents a metal cation of (1+m) valence. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. As the above R1, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 4-biphenyl group, a 2-biphenyl group or the like can be mentioned. It can be used as R3 (for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc.) Among the above phosphorus compounds, when a compound having an aromatic structure is used, It is preferable to increase the effect of improving physical properties and catalytic activity. In the above formula (Chemical Formula 17), when lanthanide is used from Li, Na, K, Be, Mg, Sr, Ba, Μη, Ni, Cu When it is selected from Zn or the like, it is preferable because the effect of improving the physical properties and the catalytic activity is increased, and among them, Li, Na, and Mg are preferably used as the metal salt compound of the phosphorus of the present invention. For example, for example, [(p-naphthyl)methylphosphonic acid ethyl]lithium, [(1-naphthyl)methylphosphonic acid ethyl] sodium, bis[(1-naphthyl)methylphosphonic acid B Magnesium, [(2-naphthyl)methylphosphonic acid ethyl]potassium, bis[(2-naphthyl)methylphosphonic acid ethyl]magnesium, [benzylphosphonate ethyl]lithium, [benzyl Sodium ethyl phosphonate, bis[benzylphosphonateethyl]magnesium, bis[benzylphosphonateethyl]indole, bis[benzylphosphonateethyl]indole, bis[benzylphosphonateethyl]manganese , sodium benzylphosphonate, magnesium bis[benzylphosphonate], [(9-fluorenyl)methylphosphonic acid-59- 1276646 V. Description of the invention (58) Ethyl] sodium, bis[(9-fluorenyl)methylphosphonic acid ethyl]magnesium, [4-hydroxybenzyl Sodium ethyl phosphonate, bis[4-hydroxybenzylphosphonic acid ethyl]magnesium, [4-chlorobenzylphosphonic acid phenyl] sodium, bis[4-chlorobenzylphosphonic acid ethyl]magnesium, [4-Aminobenzylphosphonic acid methyl] sodium, bis[4-aminobenzylphosphonic acid methyl]magnesium, sodium phenylphosphonate, bis[phenylphosphonateethyl]magnesium, di[phenyl] Phosphonic acid ethyl]zinc, etc. Among them, it is preferably [(1-naphthyl)methylphosphonic acid ethyl]lithium, [(1-naphthyl)methylphosphonic acid ethyl] sodium, two [(1- Naphthyl)methylphosphonic acid ethyl]magnesium, [benzylphosphonic acid ethyl]lithium, [benzylphosphonate ethyl]sodium, bis[benzylphosphonateethyl]magnesium, phenylphosphonate, two [Phenylphosphonic acid] Magnesium. Among the above phosphorus compounds, in the present invention, it is preferred to use phosphorus having at least one P-OH bond as a phosphorus compound. The effect of improving the physical properties of the target polyester of the present invention is increased, and when the polymerization of the polyester is found, the aluminum compound of the present invention coexists with the phosphorus compound. The effect of enhancing the activity of the catalyst is increased. The phosphorus compound having at least one P-OH bond is not particularly limited to a phosphorus compound having at least one P-OH bond in the molecule. In the case of using a phosphorus compound having at least one P-OH bond, it is preferable to improve the effect of improving the physical properties and the catalytic activity of the polyester. Among the above phosphorus compounds, a compound having an aromatic ring structure is used. Further, it is also preferable to increase the effect of improving physical properties and catalytic activity, and further, the phosphorus compound having at least one P-OH bond of the present invention is represented by the following formula (Chemical Formula 18). The compound is suitable because it can improve the physical properties of -60-1276646, and the effect of improving the catalytic activity of the invention (59). R 1 —(CH 2 ) n − 〒 1 〇 HOR 2 (In the formula (Chem. 18), R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group or an alkoxy group or an amine group; The carbon number of the group is 1 to 50. R2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms, and the η system represents an integer of 1 or more. It may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group.) As the above R1, for example, a phenyl group, a 1-naphthyl group, or 2 -naphthyl, 9-fluorenyl, 4-biphenylyl, 2-biphenylyl, and the like. As the above R2, for example, hydrogen, methyl, ethyl, propyl, isopropyl, η-butyl, t-butyl, t-butyl, long-chain aliphatic groups, Phenyl, naphthyl, substituted phenyl or naphthyl, a group represented by CH2CH20H. When a compound having an aromatic ring structure is used as the phosphorus compound, the effect of improving physical properties and catalytic activity can be increased, which is also suitable. It can be used as the phosphorus compound having at least one P-0H bond of the present invention, for example, ethyl (1-naphthyl)methylphosphonate, (1-naphthyl)methylphosphonic acid, (2) -naphthyl)ethyl methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-fluorenyl)methylphosphonate, ethyl 4-hydroxybenzylphosphonate, 2-methylbenzyl Ethyl phosphinate, phenyl 4-benzylphosphonate, methyl 4-aminobenzylphosphonate, 4-61- 1276646 5. Description of the invention (60) Ethyl methoxybenzylphosphonate and the like. Among them, ethyl (1-naphthyl)methylphosphonate, ethyl benzylphosphonate and the like are preferable. It can be used as a preferred phosphorus compound of the present invention, for example, a compound represented by the chemical formula (Chem. 19) and the like. R1 — CH2 — P (=〇) (OR2 ) (OR3 ) (In the formula (Chem. 19), R1 represents hydrogen, a hydrocarbon group having a carbon number of 1 to 49, a hydroxyl group or a halogen group or an alkoxy group. The hydrocarbon group having a carbon number of 1 to 49, and R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a hydrocarbon group having 1 to 50 carbon atoms having a hydroxyl group or an alkoxy group. Further, it may be an alicyclic structure or a branched structure containing a cyclohexyl group or the like, or an aromatic ring structure such as a phenyl group or a naphthyl group.) Further, it is more preferably a compound having at least one aromatic ring structure among R1, R2 and R3. Specific examples of such a phosphorus compound are as follows. [化 2 0]
〇C2h5〇C2h5
BPADE -62- 1276646 五、發明說明（61 [化2 1]BPADE -62- 1276646 V. Description of invention (61 [Chem. 2 1]
〇II ch2—P—OC2H5 OC2H5〇II ch2—P—OC2H5 OC2H5
NMPANMPA
[化2 2] -P- OC2H5[Chem. 2 2] -P- OC2H5
2-NMPA •63- 1276646 五、發明說明（62) [化2 3]2-NMPA •63- 1276646 V. Description of invention (62) [Chem. 2 3]
OC2H5OC2H5
AMPAAMPA
[化2 4][Chem. 2 4]
〇 CH2—P—OC2H5 GC2H54PBPADE〇 CH2—P—OC2H5 GC2H54PBPADE
[化2 5][Chem. 2 5]
OC2H5 2PBPADE 又，本發明之磷化合物，較宜是一種在聚合時難以餾去 大分子量物之效果變大者。 用來做爲本發明之磷化合物者，較宜是在同一分子內具 有苯酚部之磷化合物。又，本發明之磷化合物較宜是與苯 -64- 1276646 五、發明說明（63) 酚系化合物相互鍵結之化合物，也就是說，是在同一分子 內具有苯酚部之磷化合物。以含在同一分子內具有苯酚部 之磷化合物，除了提高本發明目標聚酯物性之改善效果， 尙且在使用在同一分子內具有苯酚部之磷化合物來聚合聚 酯時，可使觸媒活性之提高效果變大，從而聚酯之生產性 亦優良。在使用在同一分子內具有苯酚部之磷化合物來聚 合聚酯時，其在含量，即聚酯中鋁原子與磷原子之含量， 必須是在本發明之申請專利範圍內。 可做爲在同一分子內具有苯酚部之磷化合物者，雖然並 沒有特別地限定爲具有苯酚構造之磷化合物，但較宜是使 用在同一分子內具有苯酚部之自膦酸系化合物、次膦酸系 化合物、氧化膦系化合物、亞膦酸系化合物、三價膦酸系 化合物、膦系化合物中所選出之一種或二種以上之化合物 ，以使得改善聚酯之物性與觸媒活性之提昇效果變大。其 中，使用在同一分子內具有一種或二種以上之苯酚部之膦 酸系化合物時，由於可改善聚酯之物性與觸媒活性之提昇 效果變大，因而較佳。 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，較宜是以下述通式（化26)〜（化28)所代表之化合物。 -65- 1276646 五、發明說明（64) [化2 6] P (=0) R1 (OR2 ) (OR3 ) [化2 7] P (-0) R1 R4 (OR2 ) [化2 8] P (=0) R1 R5 R6 (在式（化26)〜（化28)中，R1係代表含苯酚部之碳數 爲1〜50之烴基、含有羥基或鹵素基或烷氧基或胺基等之 取代基及苯酚部之碳數爲1〜50之烴基。R4、R5、R6係各自 獨立地代表氫、碳數爲1〜50之烴基、含有羥基或鹵素基 或烷氧基或胺基等之取代基之碳數爲1〜50之烴基。R2、R3 係各自獨立地代表氫、碳數爲1〜50之烴基、含有羥基或 烷氧基等之取代基之碳數爲1〜50之烴基。但是，烴基也 可以含有環己基等之脂環構造或分枝構造或苯基或萘基等 之芳香環構造。R2與R4之末端彼此鍵結也可以。） 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，舉例來說，例如是P-羥苯基膦酸、P-羥苯基膦酸二甲酯 、P-羥苯基膦酸二乙酯、P-羥苯基膦酸二苯基酯、二（P_ 羥苯基）次膦酸、二（p-羥苯基）次膦酸甲酯、二（p-羥苯基） 次膦酸苯酯、P-羥苯基苯基次膦酸、P-羥苯基苯基次膦酸 -66- 1276646 五、發明說明（65) 甲酯、P-羥苯基苯基次膦酸苯酯' P-經苯基次膦酸' P-經 苯基次膦酸甲酯、P-羥苯基次膦酸苯酯、二（P-經苯基）膦 氧化物、三（P -羥苯基）膦氧化物、二（p -羥苯基）甲基膦苯 酯、及以下述式（化29)〜（化32)所代表之化合物等。其 中’較宜是以下述式（化3 1 )所代表之化合物，及[羥苯 基膦酸二甲酯。 [化2 9]OC2H5 2PBPADE Further, the phosphorus compound of the present invention is preferably one which has a large effect of being difficult to distill off a large molecular weight at the time of polymerization. The phosphorus compound used in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. Further, the phosphorus compound of the present invention is preferably a compound which is bonded to a phenol compound such as benzene-64-1276646, and the invention (63), that is, a phosphorus compound having a phenol moiety in the same molecule. The phosphorus compound having a phenol moiety in the same molecule can improve the physical properties of the polyester of the present invention, and can be used to polymerize the polyester when a phosphorus compound having a phenol moiety in the same molecule is used to polymerize the polyester. The effect of the improvement is increased, and the productivity of the polyester is also excellent. In the case of using a phosphorus compound having a phenol moiety in the same molecule to polymerize a polyester, its content, i.e., the content of aluminum atoms and phosphorus atoms in the polyester, must be within the scope of the present invention. In the case of a phosphorus compound having a phenol moiety in the same molecule, although it is not particularly limited to a phosphorus compound having a phenol structure, it is preferred to use a phosphonic acid compound having a phenol moiety in the same molecule, and a phosphine. One or more selected from the group consisting of an acid compound, a phosphine oxide compound, a phosphinic acid compound, a trivalent phosphonic acid compound, and a phosphine compound, so as to improve the physical properties and catalytic activity of the polyester. The effect becomes bigger. When a phosphonic acid compound having one or more phenolic moieties in the same molecule is used, the effect of improving the physical properties and catalytic activity of the polyester is improved, which is preferable. The phosphorus compound having a phenol moiety in the same molecule of the present invention can be used, and it is preferably a compound represented by the following formula (26) to (28). -65- 1276646 V. INSTRUCTIONS (64) [Chem. 2 6] P (=0) R1 (OR2) (OR3) [Chem. 2 7] P (-0) R1 R4 (OR2) [Chem. 2 8] P ( =0) R1 R5 R6 (In the formula (Chem. 26) to (Chem. 28), R1 represents a hydrocarbon group having a phenol group of 1 to 50 carbon atoms, a hydroxyl group or a halogen group or an alkoxy group or an amine group, etc. The substituent group and the phenol moiety have a hydrocarbon group of 1 to 50. R4, R5 and R6 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group or an alkoxy group or an amine group. The substituent has a hydrocarbon group of 1 to 50. R2 and R3 each independently represent a hydrogen group, a hydrocarbon group having 1 to 50 carbon atoms, a substituent having a hydroxyl group or an alkoxy group, and the like, and a hydrocarbon group having 1 to 50 carbon atoms. However, the hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. The ends of R2 and R4 may be bonded to each other.) It may be the same in the present invention. The phosphorus compound having a phenol moiety in the molecule is, for example, P-hydroxyphenylphosphonic acid, dimethyl P-hydroxyphenylphosphonate, diethyl P-hydroxyphenylphosphonate, P-hydroxybenzene. Diphenyl phosphinate, di(P-hydroxybenzene) Phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, P-hydroxyphenylphenylphosphinic acid, P-hydroxyphenylbenzene Phosphine-66- 1276646 V. Description of the invention (65) Methyl ester, P-hydroxyphenylphenylphosphinic acid phenyl ester 'P-Phenylphosphinic acid' P-Phenyl phenylphosphinate , P-hydroxyphenylphosphinic acid phenyl ester, di(P-phenyl)phosphine oxide, tris(P-hydroxyphenyl)phosphine oxide, bis(p-hydroxyphenyl)methylphosphonate, And a compound represented by the following formula (29) to (32). Among them, a compound represented by the following formula (Chemical Formula 3), and [dimethyl hydroxyphenylphosphonate are preferred. [Chem. 2 9]
[化 3 0][化3 0]
•67- 1276646 五、發明說明（的) [化3 1]•67- 1276646 V. Description of invention [of 3 1]
[化3 2][化3 2]
做爲上述式（化3 1 )所代表之化合物者，係可以使用 SANKO-220 (三光股份有限公司製）。 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，也較宜是以下述通式（化33 )爲代表之特定磷金屬化合物 中所選取之至少一種。 -68- 1276646 五、發明說明（π)As a compound represented by the above formula (Chemical Formula 3), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used. The phosphorus compound having a phenol moiety in the same molecule of the present invention may be at least one selected from the group consisting of specific phosphorus metal compounds represented by the following formula (33). -68- 1276646 V. Description of invention (π)
(在式（化33)中，ri、r2係各自獨立地代表氫、碳數爲 1〜30之烴基。R3係代表氫、碳數爲1〜5〇之烴基、含有羥 基或烷氧基之碳數爲1〜50之烴基。R4係代表氫、碳數爲 卜50之烴基、含有羥基或烷氧基或羰基之碳數爲1〜5〇之 烴基。可做爲R40·者，舉例來說，例如是氫氧化物離子、 烷酯離子、乙酸鹽離子、或乙醯酮離子等。1係1以上之 整數；m爲代表0或1以上之整數；1 +m係在4以下。Μ係 代表（1 +ΙΏ)價之金屬陽離子、η係代表1以上之整數。烴基 也可以含有環己基等之脂環構造或分枝構造或苯基或萘基 等之芳香環構造。） 其中，也較宜是自以下述通式（化34)爲代表之化合物中 所選取之至少一種。 [:化3 4](In the formula (33), ri and r2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 represents hydrogen, a hydrocarbon group having 1 to 5 carbon atoms, and a hydroxyl group or alkoxy group. a hydrocarbon group having a carbon number of 1 to 50. R4 represents a hydrogen group, a hydrocarbon group having a carbon number of 50, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group having a carbon number of 1 to 5 Å. It can be used as an example of R40. For example, it is a hydroxide ion, an alkylate ion, an acetate ion, or an ketone ion, etc. 1 is an integer of 1 or more, m is an integer of 0 or 1 or more, and 1 + m is 4 or less. The metal cation of the (1 + ΙΏ) valence and the η system represent an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. It is also preferred to use at least one selected from the group consisting of compounds represented by the following formula (34). [:3 4]
-69· 1276646 五、發明說明（68) 在式（化34)中，Mn +係代表η價之金屬陽離子、η係代 表 1、2、3 或 4。 在述式（化33)或式（化34)中，當Μ係使用自Li、Na、Κ 、：Be、Mg、Sr、Ba、Μη、Ni、Cu、Zn 等中選取之物時，由 於可使改善物性與觸媒活性之效果變大，因而較適宜。其 中’更宜是Li、Na、Mg。 可做爲本發明之特定的磷金屬鹽物者，舉例來說，例如 是[3,5-二-第三-丁基-4-羥苄基膦酸乙基]鋰、[3,5-二-第三-丁基-4-羥苄基膦酸乙基]鈉、[3, 5-二-第三-丁基-4 -羥苄基膦酸]鈉、[3，5 -二-第三-丁基-4 -羥苄基膦酸乙 基]鉀、二[3, 5-二-第三-丁基-4-羥苄基膦酸乙基]鎂、二 [3，5-二-第三-丁基-4-羥苄基膦酸]鎂、二[3, 5-二-第三-丁基·4 -羥苄基膦酸甲基]鈹、二[3, 5_二-第三-丁基-4-羥 苄基膦酸乙基]緦、二[3，5 -二:-第三-丁基-4 -羥；基膦酸 苯基]鋇、二[3, 5-二-第三-丁基-4-羥苄基膦酸乙基]錳、 二[3, 5-二-第三-丁基-4-羥苄基膦酸乙基]鎳、二[3, 5-二 -第三-丁基-4-羥苄基膦酸乙基]銅、二[3, 5-二-第三-丁 基-4-羥苄基膦酸乙基]鋅等。其中，較宜是[3, 5 -二-第 三-丁基-4-羥苄基膦酸乙基]鋰、[3, 5 -二-第三-丁基- 4-羥苄基膦酸乙基]銅、二[3, 5-二-第三-丁基-4-羥苄基膦 酸乙基]鎂。 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，也較宜是以下述通式（化35)爲代表之具有至少一個Ρ- -70- 1276646 五、發明說明（69) 0H鍵之特定磷金屬化合物中所選取之至少一種。 [化 3 5]-69· 1276646 V. INSTRUCTION DESCRIPTION (68) In the formula (34), Mn + represents a metal cation of η valence, and η represents a 1, 2, 3 or 4. In the above formula (Chem. 33) or (Formula 34), when the lanthanide series is selected from Li, Na, Κ, :Be, Mg, Sr, Ba, Μη, Ni, Cu, Zn, etc., It is preferable to increase the effect of improving physical properties and catalytic activity. Among them, 'more suitable is Li, Na, Mg. It can be used as a specific phosphorus metal salt of the present invention, for example, [3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]lithium, [3,5- Sodium di-t-butyl-4-hydroxybenzylphosphonate, sodium [3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid], [3,5-di- Third-butyl-4-hydroxybenzylphosphonic acid ethyl]potassium, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]magnesium, bis[3,5- Di-t-butyl-4-hydroxybenzylphosphonic acid]magnesium, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid methyl]pyrene, two [3, 5_ Di-t-butyl-4-hydroxybenzylphosphonic acid ethyl]anthracene, bis[3,5-di:-third-butyl-4-hydroxyl; phosphinic acid phenyl] fluorene, di[3] , 5-di-t-butyl-4-hydroxybenzylphosphonic acid ethyl]manganese, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]nickel, two [3, 5-di-t-butyl-4-hydroxybenzylphosphonic acid ethyl]copper, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]zinc Wait. Among them, it is preferably [3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]lithium, [3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid Ethyl]copper, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]magnesium. It can be used as the phosphorus compound having a phenol moiety in the same molecule of the present invention, and is preferably represented by the following formula (35) having at least one Ρ-70-1276646. 5. Description of the invention (69) 0H At least one selected from the group consisting of a specific phosphorus metal compound. [化3 5]
(在式（化35)中，R1、！^係各自獨立地代表氫、碳數爲 1〜30之烴基。R3係代表氫、碳數爲1〜5〇之烴基、含有羥 基或烷氧基之碳數爲1〜50之烴基。η係代表1以上之整數 。烴基也可以含有環己基等之脂環構造或分枝構造或苯基 或萘基等之芳香環構造。） 其中，也較宜是自以下述通式（化36)爲代表之化合物中 所選取之至少一種。 [化3 6](In the formula (35), R1, !^ each independently represents hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 represents hydrogen, a hydrocarbon group having 1 to 5 carbon atoms, and a hydroxyl group or alkoxy group. The carbon number is a hydrocarbon group of 1 to 50. The η system represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. It is preferably at least one selected from the group consisting of compounds represented by the following formula (Chem. 36). [Chem. 3 6]
(在式（化36)中，R3係代表氫、碳數爲1〜50之烴基、 含有羥基或烷氧基之碳數爲idO之烴基。烴基也可以含 有環己基等之脂環構造或分枝構造或苯基或萘基等之芳香 環構造。） 可做爲上述R3之例子者、舉例來說，例如是氫、甲基、 1276646 五、發明說明（70) 乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基、長 鏈之脂肪族基、苯基、萘基、經取代之苯基或萘基、以 CH2CH2OH所代表之基。 可做爲本發明之具有係少一個Ρ-0Η鍵之特定的磷化合 物者，舉例來說，例如是3，5 -二-第三-丁基-4 -羥苄基膦 酸乙酯、3,5-二-第三-丁基-4-羥苄基膦酸甲酯、3,5_二-第三-丁基-4-羥苄基膦酸異丙酯、3,5-二-第三-丁基- 4-羥苄基膦酸苯酯、3，5-二-第三-丁基-4-羥苄基膦酸十八 酯、3,5 -二·第三-丁基-4-羥苄基膦酸等。其中，較宜是 3，5-二-第三-丁基-4-羥苄基膦酸乙酯、3，5-二-第三·丁 基-4 -羥苄基膦酸甲酯。 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，較宜是以下述通式（化37)所代表化合物中選出之至少一 種的磷化合物。 [化3 7](In the formula (36), R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group and having a carbon number of idO. The hydrocarbon group may contain an alicyclic structure or a fraction of a cyclohexyl group or the like. A branched structure or an aromatic ring structure such as a phenyl group or a naphthyl group.) It can be exemplified as the above R3, for example, hydrogen, methyl, 1276646, and the invention (70) ethyl, propyl, and iso A propyl group, an η-butyl group, a second butyl group, a tert-butyl group, a long-chain aliphatic group, a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, and a group represented by CH2CH2OH. It can be used as a specific phosphorus compound having one Ρ-0Η bond of the present invention, for example, ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3 , methyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di- Phenyl tributyl- 4-hydroxybenzylphosphonate, octadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di-tertiary-butyl 4-hydroxybenzylphosphonic acid and the like. Among them, preferred is ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-t-butyl-butyl-4-hydroxybenzylphosphonate. The phosphorus compound having a phenol moiety in the same molecule of the present invention is preferably a phosphorus compound selected from at least one of the compounds represented by the following formula (37). [化3 7]
(在式（化37)中，R1、R2係各自獨立地代表氫、碳數爲 1〜30之烴基。R3、R4係各自獨立地代表氫、碳數爲1〜50 之烴基、含有羥基或烷氧基之碳數爲1〜50之烴基。η係代 表1以上之整數。烴基也可以含有環己基等之脂環構造或 分枝構造或苯基或萘基等之芳香環構造。） -72- 1276646 五、發明說明（71) 上述通式（化37)中，使用從下述通式（化38)所代表之 化合物中選取之至少一種，可使提高對聚酯之物性改善效 果及觸媒活性之提昇效果，因而較佳。 [化3 8](In the formula (37), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 and R4 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydroxyl group or The alkoxy group has a hydrocarbon group of 1 to 50. The η group represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. 72- 1276646 V. INSTRUCTION DESCRIPTION OF THE INVENTION (71) In the above formula (37), at least one selected from the group consisting of the compounds represented by the following formula (38) can improve the physical properties of the polyester and The effect of improving the activity of the catalyst is therefore preferred. [化3 8]
(在式（化38)中，R3、R4係各自獨立地代表氫、碳數爲 1〜50之烴基、含有羥基或烷氧基之碳數爲1〜50之烴基。 烴基也可以含有環己基等之脂環構造或分枝構造或苯基或 萘基等之芳香環構造。R2與R4之末端彼此鍵結也可以。） 可做爲上述R3、R4之例子者、舉例來說，例如是氫、甲 基、乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基 、長鏈之脂肪族基、苯基、萘基、經取代之苯基或萘基、 以CH2CH2OH所代表之基。 可做爲本發明之特定的磷化合物者，舉例來說，例如是 3, 5 -二·第三-丁基-4-羥苄基膦酸二異丙酯、3,5 -二-第三 -丁基-4-羥苄基膦酸二-η-丁酯、3,5-二-第三-丁基-4-羥 苄基膦酸雙十八酯、3,5-二-第三-丁基-4-羥苄基膦酸二 苯酯等。其中，較宜是3, 5 -二·第三-丁基-4-羥苄基膦酸 雙十八酯、3,5 -二-第三-丁基-4-羥苄基膦酸二苯酯。 可做爲本發明之在同一分子內具有苯酚部之磷化合物者 ，較宜是以下述通式（化3 9 )、(化40)所代表化合物中選 -73- 1276646 五、發明說明（72) 出之至少一種的磷化合物。 [化3 9](In the formula (38), R3 and R4 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. The hydrocarbon group may also contain a cyclohexyl group. An alicyclic structure or a branched structure or an aromatic ring structure such as a phenyl group or a naphthyl group. The ends of R2 and R4 may be bonded to each other.) Examples of the above R3 and R4 may be, for example, Hydrogen, methyl, ethyl, propyl, isopropyl, η-butyl, t-butyl, t-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthalene Base, represented by CH2CH2OH. It can be used as a specific phosphorus compound of the present invention, for example, 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid diisopropyl ester, 3,5-di-third -butyl-4-hydroxybenzylphosphonic acid di-n-butyl ester, 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-third - butyl 4-hydroxybenzylphosphonic acid diphenyl ester or the like. Among them, it is preferably 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid diphenyl ester. It can be used as the phosphorus compound having a phenol moiety in the same molecule of the present invention, and it is preferably selected from the following formulas (Chemical Formula 3) and (Chem. 40) - 73-1276646. At least one of the phosphorus compounds. [化3 9]
〇 II -P—0C〇 II -P—0C
[化 4 0] 〇c2h5[化 4 0] 〇c2h5
可使用來做爲上述化學式（化39)所示之化合物者，係有 市售之Irganox 1 222 (汽巴•特殊化學品製造公司製）； 而可做爲上述化學式（化3 9 )所示之化合物者，係有市售之 Irganox 1 425 (汽巴•特殊化學品製造公司製）。 可做爲本發明之磷化合物者，較宜是自磷化合物之鋁鹽 中所選出之至少一種。又，在本發明之聚酯中所含的鋁化 合物與磷化合物，較宜是自磷化合物之鋁鹽中所選出之至 少一種。藉由含有此種磷化合物之鋁鹽，除了能提高改良 本發明目標聚酯之物性效果，尙且在聚合聚酯中共存使用 此種磷化合物之鋁鹽時，可發現會提高觸媒之活性，從而 聚酯之生產性也優良。也可以和磷化合物之鋁鹽以外之其 他的鋁化合物、磷化合物、或苯酚系化合物共存使用。在 使用磷化合物之鋁鹽的情況下，其含量，即聚酯中鋁原子 和磷原子之含量必須是在本發.明之申請專利範圍內。 -74- 1276646 五、發明說明（73) 所謂磷化合物之鋁鹽，並沒有特別地限定爲具有鋁部之 磷化合物；但較宜是使用膦酸系化合物之鋁鹽，以使聚_ 之物性效果及觸媒之活性提高。磷化合物之鋁鹽，較宜是 含單鋁鹽、雙錦鹽、三鋁鹽等。 上述磷化合物之鋁鹽中，也較宜是使用具有芳香環構造 之化合物，以使聚酯之物性效果及觸媒之活性提高。 可做爲本發明之磷化合物之鋁鹽者，較宜是使用以下述 通式（化41)所代表之化合物中選取之至少一種，以使聚酯 之物性效果及觸媒之活性提高。 W匕4 1]As the compound represented by the above chemical formula (Chem. 39), commercially available Irganox 1 222 (manufactured by Ciba Specialty Chemicals Manufacturing Co., Ltd.) can be used as the above chemical formula (Chemical Formula 39). For the compound, there is a commercially available Irganox 1 425 (manufactured by Ciba Specialty Chemicals Manufacturing Co., Ltd.). It can be used as the phosphorus compound of the present invention, and is preferably at least one selected from the aluminum salts of the phosphorus compound. Further, the aluminum compound and the phosphorus compound contained in the polyester of the present invention are preferably at least one selected from the aluminum salts of the phosphorus compound. By the aluminum salt containing such a phosphorus compound, in addition to improving the physical properties of the target polyester of the present invention, and the use of the aluminum salt of the phosphorus compound in the polymerization of the polyester, it is found that the activity of the catalyst is increased. Therefore, the productivity of the polyester is also excellent. It may be used in combination with other aluminum compounds, phosphorus compounds or phenol compounds other than the aluminum salt of the phosphorus compound. In the case of using an aluminum salt of a phosphorus compound, the content thereof, that is, the content of the aluminum atom and the phosphorus atom in the polyester must be within the scope of the patent application of the present invention. -74- 1276646 V. Inventive Note (73) The aluminum salt of the phosphorus compound is not particularly limited to a phosphorus compound having an aluminum portion; however, it is preferred to use an aluminum salt of a phosphonic acid compound to make the physical property of the poly- The effect and activity of the catalyst are increased. The aluminum salt of the phosphorus compound is preferably a single aluminum salt, a double gold salt or a tri aluminum salt. In the aluminum salt of the above phosphorus compound, it is preferred to use a compound having an aromatic ring structure to improve the physical properties of the polyester and the activity of the catalyst. As the aluminum salt of the phosphorus compound of the present invention, it is preferred to use at least one selected from the compounds represented by the following formula (Chemical Formula 41) to improve the physical properties of the polyester and the activity of the catalyst. W匕4 1]
(在式（化41)中，R1係代表氫、碳數爲卜“之烴基、含 有羥基或鹵素基或烷氧基或胺基之碳數爲1〜50之烴基。 R2係代表氫、碳數爲1〜50之烴基、含有羥基或烷氧基之 碳數爲1〜50之烴基。R3係代表氫、碳數爲1〜5〇之烴基、 含有經基或院氧基或幾基之碳數爲1〜5〇之烴基。1係代表 1以上之整數；m爲代表〇或1以上之整數；丨+m係爲3。 η係代表1以上之整數。烴基也可以含有環己基等之脂環 構造或分枝構造或苯基或萘基等之芳香環構造。） 可做爲上述R1者，舉例來說，例如是苯基、丨_萘基、2- 萘基、9-蒽基、4-聯苯基、2-聯苯基等。可做爲上述R2者 -75- 1276646 五、發明說明（74) ，舉例來說，例如是氫、甲基、乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基、長鏈之脂肪族基、苯基、萘 基、經取代之苯基或萘基、以-CH2CH2OH所代表之基。可 做爲R3(T者，舉例來說，例如是氫氧化物離子、烷酯離子 、乙酸鹽離子、或乙醯酮離子等。 用來做爲本發明之磷化合物的鋁鹽者，舉例來說，例如 是 （1-萘基）甲基膦酸乙酯之鋁鹽、（1-萘基）甲基膦酸之 鋁鹽、（2-萘基）甲基膦酸乙酯之鋁鹽、苄基膦酸乙酯之鋁 鹽、苄基膦酸之鋁鹽、（9-蒽基）甲基膦酸乙酯之鋁鹽、4-羥基苄基膦酸乙酯之鋁鹽、2-甲基苄基膦酸乙酯之鋁鹽、 4 -氯化苄基膦酸苯酯之鋁鹽、4 -胺基苄基膦酸甲酯之鋁鹽 、4_甲氧基苄基膦酸乙酯之鋁鹽、苯基膦酸乙酯之鋁鹽等 。其中，較宜是（1-萘基）甲基膦酸乙酯之鋁鹽、苄基膦酸 乙酯之鋁鹽。 可做爲本發明之磷化合物之鋁鹽者，較宜是自具苯酚構 造的磷化合物之鋁鹽中所選出之至少一種。又，在本發明 之聚酯中所含的鋁化合物與磷化合物和苯酚系化合物，較 宜是自具有苯酚構造的磷化合物之鋁鹽中所選出之至少一 種。藉由含有此種具有苯酚構造的磷化合物之鋁鹽，除了 能提高改良本發明目標聚酯之物性效果’尙且在聚合聚酯 中共存使用此種具有苯酚構造的磷化合物之鋁鹽時，可發 現會提高觸媒之活性’從而聚酯之生產性也優良。也可以 和具有苯酚構造的磷化合物之鋁鹽以外之其他的鋁化合物 -76- 1276646 五、發明說明（75) 、磷化合物、或苯酚系化合物共存使用。在使用具有苯酚 構造的磷化合物之鋁鹽的情況下，其含量，即聚酯中鋁原 子和磷原子之含量必須是在本發明之申請專利範圍內。 可做爲本發明之具有苯酚構.造的磷化合物之鋁鹽者，較 宜是使用以下述通式（化42)所代表之化合物中選取之至少 一種。 [化 4 2](In the formula (Formula 41), R1 represents a hydrocarbon group having a carbon number of "hydrocarbon group", a hydroxyl group or a halogen group or an alkoxy group or an amine group having a carbon number of 1 to 50. R2 represents hydrogen or carbon. a hydrocarbon group having a hydrocarbon group of 1 to 50 and a hydrocarbon group having a hydroxyl group or an alkoxy group of 1 to 50. R 3 represents a hydrogen group, a hydrocarbon group having a carbon number of 1 to 5 Å, and a group having a trans group or an oxime group or a group. The hydrocarbon group having a carbon number of 1 to 5 Å. The 1 system represents an integer of 1 or more; m represents an integer of 1 or more; 丨+m is 3. The η represents an integer of 1 or more. The hydrocarbon group may also contain a cyclohexyl group or the like. An alicyclic structure or a branched structure or an aromatic ring structure such as a phenyl group or a naphthyl group.) The above R1 may be, for example, a phenyl group, a fluorene-naphthyl group, a 2-naphthyl group, or a 9-fluorene group. a group, a 4-biphenyl group, a 2-biphenyl group, etc., which can be used as the above R2 -75-1276646. 5. Description of the invention (74), for example, hydrogen, methyl, ethyl, propyl, Isopropyl, η-butyl, t-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthyl, represented by -CH2CH2OH. As R3 (T, for example For example, it is a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc. The aluminum salt used as the phosphorus compound of this invention is, for example, (1-naphthyl group). An aluminum salt of ethyl methylphosphonate, an aluminum salt of (1-naphthyl)methylphosphonic acid, an aluminum salt of ethyl (2-naphthyl)methylphosphonate, an aluminum salt of ethyl benzylphosphonate , aluminum salt of benzylphosphonic acid, aluminum salt of ethyl (9-fluorenyl)methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum of ethyl 2-methylbenzylphosphonate Salt, aluminum salt of 4-phenylbenzylphosphonate, aluminum salt of methyl 4-aminobenzylphosphonate, aluminum salt of ethyl 4-methoxybenzylphosphonate, phenylphosphonic acid An aluminum salt of an ester, etc., preferably an aluminum salt of ethyl (1-naphthyl)methylphosphonate or an aluminum salt of ethyl benzylphosphonate. It can be used as the aluminum salt of the phosphorus compound of the present invention. Preferably, it is at least one selected from the aluminum salt of a phosphorus compound having a phenol structure. Further, the aluminum compound and the phosphorus compound and the phenol compound contained in the polyester of the present invention are preferably self-having a phenol structure. Aluminum of phosphorus compound At least one selected from the group consisting of the aluminum salt containing the phosphorus compound having a phenol structure, in addition to improving the physical property effect of the target polyester of the present invention, and coexisting in the polymerized polyester, the phenol structure is used. When the aluminum salt of the phosphorus compound is found, the activity of the catalyst is increased, and the productivity of the polyester is also excellent. It is also possible to use an aluminum compound other than the aluminum salt of the phosphorus compound having a phenol structure-76- 1276646. In the case where an aluminum salt having a phosphorus compound having a phenol structure is used, the content thereof, that is, the content of aluminum atoms and phosphorus atoms in the polyester must be in the present invention. Within the scope of the patent application, it is preferred to use at least one selected from the group consisting of the compounds represented by the following formula (Chem. 42) as the aluminum salt of the phosphorus compound of the present invention. [化 4 2]
(在式（化42)中，R1、R2係各自獨立地代表氫、碳數爲 1〜30之烴基。R3係代表氫、碳數爲1〜50之烴基、含有羥 基或烷氧基之碳數爲1〜50之烴基。R4係代表氫、碳數爲 1〜50之烴基、含有羥基或烷氧基或羰基之碳數爲1〜50之 烴基。1係代表1以上之整數；m爲代表0或1以上之整 數；1 +m係爲3。η係代表1以上之整數。烴基也可以含有 環己基等之脂環構造或分枝構造或苯基或萘基等之芳香環 構造。） 其中’較宜是從以下述通式（化43 )所代表之化合物中選 取‘之至少一種。 -77- 1276646 五、發明說明（76) [化4 3](In the formula (42), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a carbon group having a hydroxyl group or an alkoxy group. a hydrocarbon group of 1 to 50. R4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group having 1 to 50 carbon atoms, and 1 system represents an integer of 1 or more; m is An integer of 0 or 1 or more; 1 + m is 3. The η represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. Wherein 'it is preferably at least one selected from the group consisting of compounds represented by the following formula (Chem. 43). -77- 1276646 V. Description of invention (76) [Chem. 4 3]
(在式（化43)中，R3係代表氫、碳數爲1〜50之烴基、 含有羥基或烷氧基之碳數爲1〜50之烴基。R4係代表氫、 碳數爲1〜50之烴基、含有羥基或烷氧基或羰基之碳數爲 1〜50之烴基。1係代表1以上之整數；m爲代表〇或1以 上之整數；1+m係爲3。烴基也可以含有環己基等之脂環 構造或分枝構造或苯基或萘基等之芳香環構造。） 可做爲上述R3之例子者、舉例來說，例如是氫、甲基、 乙基、丙基、異丙基、η-丁基、第二丁基、第三丁基、長 鏈之脂肪族基、苯基、萘基、經取代之苯基或萘基、以_ CH2CH2〇H所代表之基。可做爲r4〇-者，舉例來說，例如是 氫氧化物離子、烷酯離子、乙酸鹽離子、或乙醯酮離子等 可做爲本發明之特定的磷化合物者，舉例來說，例如是 3, 5-二-第三-丁基-4-羥苄基膦酸乙酯之鋁鹽、3,5-二-第 三-丁基-4-羥苄基膦酸甲酯之鋁鹽、3,5 -二-第三-丁基- 4 -羥苄基膦酸異丙酯之鋁鹽、3,5 -二-第三-丁基-4-羥苄 基膦酸苯酯之鋁鹽、3,5-二-第三-丁基-4-羥苄基膦酸之 鋁鹽等。其中，較宜是3 ,5 -二-第三-丁基-4-羥苄基膦酸 -78- 1276646 五、發明說明（77) 乙酯之鋁鹽、3,5 -二-第三-丁基-4-羥苄基膦酸甲酯之鋁 於上述磷化合物中使用鹼金屬、鹼土金屬，或鋁之鹽的 情況下，其添加量，即在最終所得到的聚酯中鋁原子和磷 原子之含量必須是在本發明之申請專利範圍內。藉由該方 法，將可以抑制發生對聚酯不溶性之異物的效果，並改善 紡絲之切絲或成形時之過濾器阻塞等之問題。 可用來添加在本發明之聚合觸媒中之銻化合物者，舉例 來說，較適當的是三氧化銻、五氧化銻、醋酸銻、苷氧化 銻等。特佳係使用三氧化銻。又，可做爲鍺化合物者，舉 例來說，例如是二氧化鍺、四氯化鍺。特佳係使用二氧化 鍺。二氧化鍺係可使用在結晶性或非結晶性物兩方面。 又，鈦化合物、錫化合物等之其他的聚合觸媒，可做爲 鈦化合物者，舉例來說，例如是四-11 -丙基鈦、四異丙基 鈦、四-η -丁基鈦、四異丁基鈦、四-第三丁基鈦、四環己 基鈦、四苯基鈦、四苄基鈦、草酸鈦酸鋰、草酸鈦酸鉀、 草酸鈦酸錳、氧化鈦、鈦與矽、鉻、鹼金屬、鹼土金屬等 之複合氧化物、鈦之正酯或縮合正酯、鈦之正酯或縮合正 酯與羥基羧酸所成之反應生成物、鈦之正酯或縮合正酯與 羥基羧酸和磷化合物所成之反應生成物、鈦之正酯或縮合 正酯和具有至少2個羥基之多元醇，由2 -羥基羧酸及鹽基 所形成之反應生成物。其中，較宜是鈦和矽之複合氧化物 、鈦和錳之複合氧化物、鈦之正酯或縮合正酯與羥基羧酸 -79- 1276646 五、發明說明（78 ) 和磷化合物所成之反應生成物。又，做爲錫化合物者，舉 例來說，例如是二丁錫氧化物、甲基苯基錫氧化物、四乙 基錫、六乙基二錫氧化物、三乙基錫氫氧化物、單丁基羥 基錫氧化物、三異丁基錫氧化物、二苯基錫月桂酸鹽、單 丁基錫三氯化物、二丁基錫硫化物、二丁基羥基錫氧化物 、甲基錫酸、乙基錫酸等。特佳係使用單丁基羥基錫氧化 物。 本發明中所可能添加的鈷化合物，並沒有特別地限定爲 某種物質，但具體之實施例，舉例來說，例如是醋酸鈷、 硝酸鈷、氯化鈷、乙酸乙醯鈷、萘酸鈷及其水合物等。其 ，較宜是乙酸鈷四水鹽。 依照本發明之方法，在製造聚酯之際，較宜是添加苯酚 系化合物，以使增加聚酯熱安定性效果。 可做爲本發明之苯酚系化合物者，並沒有特別地限定爲 具有苯酚構造之化合物，舉例來說，例如是2,6-二·第三-丁基-4-甲基酚、2,6-二-第三-丁基-4-乙基酚、2，6-二環 己基-4-甲基酚、2，6-二異丙基-4-甲基酚、2，6-二-第三-戊基-4-甲基酚、2,6 -二-第三-辛基- 4- η·丙基酚、2,6 -二 -環己基- 4-η-辛基酚、2-異丙基-4-甲基-6-第三-丁基酚 、2-第三-丁基-2-乙基-6-第三-辛基酚、2-異丁基-4-乙 基-6-第三-己基酚、2·環己基- 4-η-丁基-6-異丙基酚、 1，1，1-三（4 -羥苯基）乙烷、1，1，3 -三（2 -甲基-4-羥基-5第 三-丁苯基）乙烷、三乙二醇-三[3-(3-第三-丁基-5-甲基- -80- 1276646 五、發明說明（79) 4 -羥基苯基）丙酸酯]、1，6 -己烷二醇-二[3-(3, 5 -二-第三 -丁基-4-羥基苯基）丙酸酯]、2,2-硫二伸乙基二[3-(3, 5-二-第三-丁基-4,4-羥基苯基）丙酸酯]、N，N’-六亞甲基二 (3, 5 -二-第三-丁基-4-羥基-氫肉桂酸化物、1，3,5 -三 (2,6-二甲基-3-羥基-4-第三-丁苄基）異氰酸酯、1，3,5-三（3,5 -二-第三-丁基-4-羥苯基）異氰酸酯、1，3,5-三 [3, 5-二-第三-丁基-4-羥苯基）丙醯基氧乙基]異氰酸酯、 三（4-第三-丁基-2,6-二甲基-3-羥苄基）異氰酸酯、2,4-二（η -辛基硫基）-6-(4 -羥基-3, 5 -二-第三-丁苯胺基）異氰 酸酯、1，3, 5-三畊、四[亞甲基（3, 5-二-第三-丁基-4-羥 基）氫肉桂酸酯]胺、二[3, 3-二（3-第三-丁基-4-羥苯基） 丁酸二醇]醚、N，N、二[3-(3,5-二-第三-丁基-4-羥苯基） 丙醯基]畊、2,2’-噚唑醯胺二[乙基- 3- (3，5 -二-第三-丁 基-4·羥苯基）丙酸酯]、二[2 -第三-丁基-4-甲基-6- (3-第三-丁基-5-甲基-2羥苄基）苯基]對酞酸酯、1，3,5-三甲 基-2，4,6-三（3, 5-二-第三-丁基-4-羥苄基）苯、3，9-二 [1，1-二甲基- 2-{θ - (3-第三-丁基-4-羥基-5-甲基苯基） 丙醯基氧}乙基]-2,4,8，10-四噚焦[5,5]十一烷、2,2-二 [4-(2-(3, 5-二-第三-丁基-4-羥基丙苯胺基氧））乙氧苯基] 丙院、沒- (3, 5 -— -弟二-丁基-4-趨苯基）丙酸院酯、四-[ 甲基-3- (3，，5，-二-第三-丁基-4-羥苯基）丙酸酯]甲烷、 十八基-3-(3，5-二-第三-丁基-4-羥苯基）丙酸酯、ι,υ-三（2 -甲基-4-羥基-5-第三-丁苯基）丁烷、硫二亞乙基-二 -81 - 1276646 五、發明說明（8〇) [3-(3，5-二-第三-丁基-4-羥苯基）丙酸酯]、伸乙基二（氧 伸乙基）二[3-(3,5-二-第三-丁基-4-羥苯基）丙酸酯、三 六一醇-二-[3-(3·-第三·丁基-5-甲基苯基）丙酸酯、 1，1，3-三（2 -甲基- 4-[3-(3,5-二-第三-丁基-4-羥苯基）丙 醯基氧]-5-第三-丁苯基）丁烷等。在此，同時使用兩者以 上也可以。其中，較宜是1，3，5-三甲基，4，6-三（3，5-二 -第三-丁基-4-羥苄基）苯、四-[甲基- 3- (3，，5’-二-第三-丁基-4-羥苯基）丙酸酯]甲烷、硫二亞乙基-二[3-(3，5 -二 -第三-丁基-4-經苯基）丙酸酯]。 本發明之苯酚系化合物較宜是具有受阻酚構造之物。 本發明之苯酚系化合物之使用量，相對於聚合所得聚酯 中的二羧酸及多元羧酸等之羧酸成分的全部構成單位之莫 耳數計，較宜是在從5 X 10·5莫耳％到1莫耳％之範圍； 更宜是在從1 X 10_4莫耳％到0.5莫耳％之範圍。 依照本發明來製造聚酯時，係可以使用向來所公知的方 法來進行。例如，當在製造PET之情況下，使對酞酸和乙 二醇之酯化後、再予以重縮合之方法，或者對酞酸二甲酯 等對酞酸之烷酯、與乙二醇間進行酯化交換反應後、再予 以重縮合之方法，係可以使用其中任一者之方法來進行。 又，聚合裝置可以是批式，連續式也可以。 依照本發明之方法於聚合聚酯時所使用的觸媒，係爲不 僅對聚縮合反應之酯化反應具有觸媒活性，且對酯化交換 反該應也具有觸媒活性。對酞酸二甲酯等二羧酸之烷酯、 -82- 1276646 五、發明說明（81) 與乙二醇間之酯化交換反應，通常係在鋅等之酯化交換觸 媒存在下進行，但是可以使用本發明之觸媒來取代該種觸 媒’或者是與該等觸媒共存也可以。又，依照本發明之方 法於聚合聚酯時所使用的觸媒，係可以使用對熔融聚合、 且對固相聚合或溶液聚合均具有觸媒活性者，並可以任何 一種方法來製造聚酯。 依照本發明之方法於聚合聚酯時所使用的觸媒，係可以 在聚合反應之任意階段添加至反應系中。例如，可以在酯 化反應或酯化交換反應之開始前及反應中途的任意階段， 或者是在聚縮合反應之正好開始前及反應中途的任意階段 ，添加至反應系中。特別地，較宜是在聚縮合反應之正好 開始前添加不含鋁之化合物。 依照本發明之方法於聚合聚酯時所使用的觸媒或其他化 合物之添加方法，可以是粉末狀或捏合狀、乙二醇等溶媒 之漿液狀或溶液也可以，並沒有特別地限定。又，也可以 添加觸媒構成成分及其他化合物預先混合之物，分別添加 也可以。又，也可以添加本發明之鋁化合物的觸媒溶液及 其他化合物預先混合之混合物，分別添加也可以。又，也 可以將觸媒構成成分及其他化合物同時添加側聚合系中， 個別成分分別添加也可以。又，可以一次添加觸媒及其他 化合物，分成複數次添加也可以。 在本發明中所說的聚酯，係指由含二羧酸及多元羧酸等 之酯形成性衍生物中選出之至少一種或二種以上，與含二 -83- 1276646 五、發明說明（82) 醇之多元醇中選出之至少一種或二種以上所成之物；或者 是由羥基羧酸及其酯形成性衍生物所成之物；或是由環狀 酯所形成之物。 可做爲二羧酸者，舉例來說，例如是草酸、丙二酸、號 珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二 酸、十基二羧酸、十二基二羧酸、十四基二羧酸、十六基 二羧酸、1，3 -環丁烷二羧酸、1，3 -環戊烷二羧酸、1，2 -環 己烷二羧酸、1,3 -環己烷二羧酸、1，4-環己烷二羧酸、 2,5 -正萡烯二羧酸、雙聚物酸等之飽和脂肪族二羧酸或其 酯形成性衍生物，富馬酸、馬來酸、衣康酸等所例示之不 飽和脂肪族二羧酸或其酯形成性衍生物；鄰酞酸、異酞酸 、對酞酸、5-(鹼金屬）硫異酞酸、二苯酸、1，3 -萘二羧酸 、1，4-萘二羧酸、1，5-萘二羧酸、2,6-萘二羧酸、2,7-萘 二羧酸、4，4’-二苯基二羧酸、4，4’-二苯基硫二羧酸、 4,4、二苯醚二羧酸、1，2-二（酚氧）乙烷- ρ，ρ·-二羧酸、 棕櫚酸、蒽二羧酸等所例示之芳香族二羧酸或其酯形成性 衍生。此等二羧酸之中，較宜是對酞酸、及萘二羧酸、以 及2,6-萘二羧酸。 可做爲此等二羧酸以外之多元羧酸者，舉例來說，例如 是乙烷三羧酸、丙烷三羧酸、丁烷三羧酸、均苯四酸、偏 苯三甲酸、三羥甲酸、3，4，3 ·，4 ’ -聯苯對酞酸，及其酯形 成性衍生物。 可用來做爲二醇者，舉例來說，例如是乙二醇、1,2 -丙 -84- 1276646 五、發明說明（83) 二醇、1，3 -丙二醇、二乙二醇、三乙二醇、1，2 -丁二醇、 1，3 -丁二醇、2,3 -丁二醇、1，4 -丁二醇、1，5 -戊二醇、新 戊二醇、1，6 -己二醇、1，2 -環己二醇、1,3 -環己二醇、 1，4-環己二醇、1，2-環己二甲醇、1，3-環己二甲醇、1，4-環己二甲醇、1，4-環己二乙醇、1，1〇-十亞甲二醇、1，12-十二基二醇、聚乙二醇、聚三亞甲基二醇、聚三亞甲基二 醇等所例示之脂肪族二醇；氫醌、4,4’-羥二酚、1,4 -雙（ yS -羥基乙氧）苯、1，4-雙（々-羥基乙氧苯基）楓、雙（p-羥 苯基）醚、雙（P-經苯基）楓、雙（P-經苯基）甲院、1，2 -雙 (P -羥苯基）乙烷、聯酚A、聯酚C、2，5 -萘二醇、在此等 二醇上附加環氧乙烷之二醇等所例示之芳香族二醇；在此 等二醇之中，以使用乙二醇及1,4-丁二醇較爲理想。 可做爲此等二醇以外之多元醇者，舉例來說，例如是三. 羥甲基甲烷、三羥甲基乙烷、三羥甲基丙烷、季戊四醇、 丙三醇、己烷三醇等。 可做爲羥基羧酸者，舉例來說，例如是乳酸、枯酸、蘋 果酸、酒石酸、羥基醋酸、3 -羥基丁酸、p -羥基苯甲酸、 P-(2-羥基乙氧）苯甲酸、仁羥基環己烷羧酸、或其酯形成 性衍生物等。 環狀酯舉例來說，例如其可以是ε -己內酯、$ -丙內酯 、/3_甲基_y3_丙內酯、戊內酯、甘醇化物、丙交酯等 〇 又，在本發明之聚酯中，係可以包括以公知的磷系化合 -85- 1276646 五、發明說明（84) 物來做爲共聚合成分。磷系化合物較宜是二官能性之磷系 化合物，舉例來說，例如是苯基膦酸二甲酯、苯基膦酸二 苯酯、（2 -羧基乙基）甲基次膦酸、（2 -羧基乙基）苯基次膦 酸、（2 -甲氧羧基乙基）苯基次膦酸甲酯、（4 -甲氧羧基乙 基）苯基次膦酸甲酯、[2-(/3-羥基乙氧羰基）乙基]甲基次 膦酸之乙二醇酯、（1，2 ·二羧乙基）甲基次膦氧化物、 9，10 -二氫-10 -氧- (2,3 -羧丙基）-i〇 -膦伸苯乙醯胺基-10-氧化物等。藉由使含有此等磷系化合物做成之共聚合成分 ，將可以使所得到的聚酯之難燃性等增加。 可做爲多元羧酸或羥基羧酸之酯形成性衍生物者，舉例 來說，例如是院酯、酸氯化物、酸酐等。 在本發明中所用的聚酯，較宜是使用主要之酸成分爲對 酞酸或其酯形成性衍生物、或者萘二羧酸或其酯形成性衍 生物；主要之醇成分爲伸烷二醇之聚酯。較佳之聚酯，相 對於此種主要之酸成分爲對酞酸或其酯形成性衍生物、或 者萘二羧酸或其酯形成性衍生物之全部酸成分計，較宜是 含有對酞酸或其酯形成性衍生物以及萘二羧酸或其酯形成 性衍生物之總量在70莫耳％以上之聚酯，更宜是在8〇莫 耳％以上之聚酯，最宜是在90莫耳％以上之聚酯。主要之 醇成分爲伸烷二醇之聚酯、相對於全部之二醇成分計，較 宜是含有伸烷二醇之總量在70莫耳％以上之聚酯，更宜是 在80莫耳％以上之聚酯，最宜是在90莫耳％以上之聚酯。 此處所說的伸院二醇也可以是在分子鏈中含有取代基或脂 -86- 1276646 五、發明說明（85) 環構造者。 可做爲在本發明中所用的萘二羧酸或其酯形成性衍生物 者，舉例來說，例如較宜是1,3-萘二羧酸、1，4-萘二羧酸 、1，5-萘二羧酸、2，6-萘二羧酸、2, 7-萘二羧酸等萘二羧 酸或其酯形成性衍生物。 可做爲在本發明中所用的伸烷二醇者，係有乙二醇、 1，2-丙二醇、1，3-丙二醇、二乙二醇、三乙二醇、1，2-丁 二醇、1，3-丁 二醇、2,3-丁 二醇、1，4-丁二醇、1，5-戊二 醇、新戊二醇、1，6 -己二醇、1，2 -環己二醇、1，3 -環己二 醇、1，4-環己二醇、1，2_環己二甲醇、1，3-環己二甲醇、 1，4-環己二甲醇、1，4-環己二乙醇、1，10-十亞甲二醇、 1，12-十二基二醇等。同時使用此等之中2種以上也可以 〇 在本發明之聚酯中，可做爲對酞酸或其酯形成性衍生物 、或者萘二羧酸或其酯形成性衍生物以外之酸成分者，係 有草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛 二酸、壬二酸、癸二酸、十基二羧酸、十二基二羧酸、十 四基二羧酸、十六基二羧酸、1，3 -環丁烷二羧酸、1，3_環 戊烷二羧酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、 1，4 -環己烷二羧酸、2，5·正萡烯二羧酸、雙聚物酸等之飽 和脂肪族二羧酸或其酯形成性衍生物，富馬酸、馬來酸、 衣康酸等所例示之不飽和脂肪族二羧酸或其酯形成性衍生 物；鄰酞酸、異酞酸、對酞酸、5-(鹼金屬）硫異酞酸、二 -87- 1276646 五、發明說明（86) 苯酸、4，4，-二苯基二羧酸、4，4’-二苯基硫二羧酸、 4,4，-二苯醚二羧酸、I，2-二（酚氧）乙烷-p，p、一竣酸、 棕櫚酸、蒽二羧酸等所例示之芳香族二竣酸或其酯形成性 衍生；乙烷三羧酸、丙烷三殘酸、丁院三殘酸、均苯四酸 、偏苯三甲酸、三經甲酸、3，4,3，，4’·聯苯對酞酸’及其 酯形成性衍生物；乳酸、檸檬酸、蘋果酸、酒石酸、經基 醋酸、3 -經基丁酸、p -經基苯甲酸、P-(2 -經基乙氧）苯甲 酸、4 -羥基環己烷羧酸、或其酯形成性衍生物等。又’也 可以含有ε-己內酯、/3 -丙內酯、/3 -甲基- /3 -丙內酯、 5 -戊內酯、甘醇化物、丙交酯等所例示之環狀酯者。 在本發明之聚酯中，可做爲伸烷二醇以外之二醇成分者 ，例如是含有二乙二醇、三乙二醇、聚乙二醇、聚三亞甲 基二醇、聚四亞甲基二醇等所例示之脂肪族二醇；氫醌、 4,4、羥二酚、1，4-雙（0 -羥基乙氧）苯、1,4-雙（/3 -羥基 乙氧苯基）楓、雙（Ρ-羥苯基）醚、雙（Ρ-羥苯基）楓、雙（Ρ-羥苯基）甲烷、1，2 _雙（ρ -羥苯基）乙烷、聯酚A、聯酚C、 2，5 -萘二醇、在此等二醇上附加環氧乙烷之二醇等所例示 之芳香族二醇；三羥甲基甲烷、三羥甲基乙烷、三羥甲基 丙烷、季戊四醇、丙三醇、己烷三醇等所例示之多元醇故 爲共聚合成分者。 又，在本發明之聚酯中，係可以包括以公知的磷系化合 物來做爲共聚合成分。磷系化合物較宜是二官能性之磷系 化合物，舉例來說，例如是苯基膦酸二甲酯、苯基膦酸二 -8 8 - 1276646 五、發明說明（87) 苯酯、（2 -羧基乙基）甲基次膦酸、（2 -羧基乙基）苯基次膦 酸、（2 -甲氧羧基乙基）苯基次膦酸甲酯、（4 -甲氧羧基乙 基）苯基次膦酸甲酯、[2-(/3-羥基乙氧羰基）乙基]甲基次 膦酸之乙二醇酯、（1，2 -二羧乙基）甲基膦氧化物、9, 10-二氫-10-氧- (2,3-羧丙基）-10-膦伸苯乙醯胺基-10-氧化 物等。藉由使含有此等磷系化合物做成之共聚合成分，將 可以使所得到的聚酯之難燃性等增加。 可做爲本發明之聚酯者，較宜是聚對酞酸乙二酯、聚對 酞酸丙二酯、聚（1，4-環己烷亞甲基對酞酸酯）、聚萘酞酸 乙二酯、聚萘酞酸丁二酯、聚萘酞酸丙二酯及其共聚物； 其中，特別合宜的是聚對酞酸乙二酯及其共聚物。 爲了改善以聚做爲酯纖維使用情況下之染色性，較佳的 具體實施態樣，係以具有硫酸鈣金屬鹽基之聚羧酸做成之 共聚合成分來當做本發明聚酯之構成成分。 使用來當做共聚合單體之含有金屬之硫酸鹽基之化合物 者，並沒有特別地限定爲某種物質，舉例來說，例如是5-鈉硫異酞酸鹽、2 -鈉硫對酞酸鹽、5 -鋰硫異酞酸鹽、2 -鋰 硫對酞酸鹽、5-鉀硫異酞酸鹽、2-鉀硫對酞酸鹽、或其低 級烷酯衍生物等。在本發明中，以使用5-鈉硫異酞酸鹽或 其酯形成性衍生物特別合宜。 含有金屬硫酸鹽基化合物之.共聚合量，相對於構成聚酯 之酸成分計，宜是0.3〜10.0莫耳％，更宜是0.80〜5.0 莫耳％。當共聚合量過少時，鹽基性染料可染性會變差， -89- 1276646 五、發明說明（88) 當過多時，在做成纖維的情形下，因不僅製絲性會變得不 佳，而且增粘現象，以致所得到的纖維強度並不夠充分。 又，當以2.0莫耳％以上之含有金屬硫酸鹽基化合物來共 聚合時，可以賦予常壓可染性之經改質的聚酯纖維。又， 選擇適當的易染化單體，將可適當地減少含有金屬硫酸鹽 基化合物之使用量。可做爲易染單體，並沒有特別地限定 爲某種物質，舉例來說，例如是以聚乙二醇、聚四亞甲基 二醇爲代表之長鏈二醇化合物、或己二酸、癸二酸、壬二 酸爲代表之脂肪族二羧酸。 依照本發明之方法聚合聚酯之後，由該聚酯除去觸媒、 或藉由添加磷系化合物等使觸媒失活，將可以使聚酯之熱 安定性變得更高。 在本發明之聚酯中，其係可以包括苯酚系、芳香族胺系 等之氧化防止劑，例如，可以含有此等中之一種或二種以 上，則將可以使聚酯之熱安定性變得更高。 在本發明之聚酯中，其係可以包括附藍劑、有機系、無 機系，或有機金屬系之染料、顏料、以及螢光增白劑等； 可以含有此等中之一種或二種以上，則將可以抑制聚酯之 黃色等之著色。 在本發明之聚酯中，也可以包括其他之聚合物或安定劑 、氧化防止劑、制電劑、消泡劑、染色性改良劑、染料、 顏料、.消艷劑、其他的添加劑。 此種添加劑，係可以在聚合聚酯時或聚合後，或者是在 -90- 1276646 五、發明說明（89) 聚酯成形時的任意階段來添加.；該較適當的階段係會因聚 合物之特性、或聚酯成形體之性能要求而異。 【實施例】 以下，藉由實施例來詳細地說明本發明，但本發明並不 因此而僅限定於此等實施例而已。 在本發明實施例中所使用的評量方法係如以下所示。 (1)聚合物中金屬及磷之含量。 磷、銻及鍺之含量係以螢光X射線法來測定。將測定試 料聚酯投入置於照相用鐵製板上之5毫米、直徑40毫米 不銹鋼製環內。在烤箱內以300°C、加熱10分鐘使之熔化 。將之取出冷卻後，取出藉環成形之試樣，測定平滑那一 面。又，其他的方法，係爲化學分析方法，即以上述方法 形成預定聚酯之數個點、測定螢光X射線強度，而做成以 化學分析法所求得的値與螢光X射線之檢量線。以測定試 料聚酯之螢光X射線強度數據所成的檢量線爲基準，來計 算出各個試樣中的磷、銻、及鍺之含量。 其他的金屬含量，係以下述之方法來測定。稱取1.0克 之聚酯，在白金坩堝內，於碳化電氣爐中以550°C使之灰 化，冷卻到室溫後，以6N鹽酸（在鈦之情況下則是氟酸/ 鹽酸混合物）使之溶解，蒸發乾燥凝固後，以1.2N鹽酸使 之溶解，做成供給到高頻電漿發光分析（島津製作所製， ICPS-2000)及原子吸光分析（島津製作所製，AA- 640- 1 2) 上之試樣。又，另一方法，係使用市售的原子吸光用標準 -91 - 1276646 五、發明說明（9〇) 溶液，做成待測定每一金屬之在〇·〇1〜30毫克/升之濃度 範圍的檢量線用溶液，以高頻電漿發光分析（Al、Ca、Mg 、Co)及原子吸光分析（Na、Li、K)來進行，做成檢量線 ，以此檢量線爲基準，由每一個試樣的分析數據來計算出 聚酯中的金屬含量。 (2)聚酯之特性黏滯度（IV) 將0.1克之聚酯溶解在25毫升之苯酚/1，1，2,2-四氯乙 烷之重量比爲6/4的混合溶媒中，使用烏貝勒爾達黏度計 ，在溫度爲30°C下測定之。 (3 )酸値 將聚酯冷凍粉碎，於130°C下真空乾燥12小時以上。精 稱0.1克之試料置於試驗內，加入1〇毫升之苄醇，使之 溶解。溶解後，在水浴中使之冷卻。加入1 0毫升之氯仿 、酚酞指示劑，使用0.1N NaOH之甲醇/苄醇=1/9溶液來 滴定，後求得酸値。 (4) 二乙二醇成量（DEG) 將0.1克之聚在2毫升之甲醇中，以250°C加熱分解之 後，藉以氣相層析儀（使用島淨製作所製之GC-14B)定量而 求得。分析管柱係使用充塡在迪耶魯科學製之PEG-ΗΤ的 管柱。 (5) 示差描描式熱量分析（DSC) 使用ΤΑ儀器公司製之DSC2920來測定。將約10.0毫克 之聚酯密封在ΤΑ儀器公司製之自動取樣器用專用的鋁盆 -92- 1276646 五、發明說明（91) 內，以50 °C分/分之昇溫速度加熱至280 °C爲止，到達 280°C開始保持1分鐘後，即以液態氮淬冷之。之後，從 室溫開始以20°C/分之昇溫速度昇溫至300°C爲止，以求 得昇溫時之結晶化溫度Tel、以及熔點Tm。從到達300°C 開始保持2分鐘後，以1 0°C /分降溫，以求得降溫時之結 晶溫度Tc2。以每一個峰値之最大部分，分別做爲Tel、 Tm、Tc2之溫度。 (6)色相 使用色差計（東色電色股份有限公司製，TC- 1 500MC-88 型），來測定亨特色度之L値、a値、b値。在測定試料爲 聚酯樹脂薄片之情形下，以實施例所記載方法製得直徑約 2毫米、長度爲約3毫米之薄片，在室溫下於濾紙上風乾 約一晝夜後，使用其來測定色度。 (7 )紡絲時瓶壓上昇及拉伸時斷絲時之評量 將熔融聚合所得到之PET樹脂薄片予以乾燥後，供小至 熔融押出機上，使用20微米之過濾器，從290°C之具有孔 徑爲0.14毫米Φ之孔口共108個之紡絲口吐出，以常法 使之冷卻，加油後，以1 720公尺/分鐘引取之。繼續引取 ，以預熱80°C之輥、設定溫度爲150°C，拉伸2.127倍， 而得到47 d t ex、1 08長絲之聚酯拉伸絲。又，使用各別 不同的紡絲機台來進行實施例1〜5之評量。 根據紡絲時之濾壓上昇程度，依照如下評量之。 〇：確實認不出有濾壓上昇； -93- I276646 五、發明說明（92) △:可認出濾壓上昇； X:濾壓顯著地上昇。 根據拉伸時之斷絲頻率，依照如下評量之。 〇：確實沒有引起斷絲； △:有引起斷絲； X :發生多起斷絲。 (8) 熱安定性參數（TS) 將1克之熔融聚合之IV爲0.64〜0.66 dl/克（熔融 試驗前：[IVh)之PET樹脂薄片，置入內徑約爲14毫米 之玻璃試驗管中，以130°C真空乾燥12小時後，接著對在 真空管路上之玻璃試驗管減壓、並封入氮氣反復操作5次 以上後，以100托利封入氮氣再封管。使該試驗管浸漬在 300°C之鹽浴中，維持在熔融狀態2小時後，取出試樣予 以冷凍粉碎、真空乾燥後，測定IV (熔融試驗前：[IV]f) 。使用下述計算式從該[IV]f求得TS。此式係引用文獻（上 山拉：日本橡膠協會第63卷第8號第497頁，1 990年）。 TS = 0.245 { [IVV1.47 - [IV]，.47 } (9) 熱氧化安定性參數（TOS) 將熔融聚合之IV爲0.64〜0.66 dl/克（熔融試驗前： [IVh)之PET樹脂薄片，藉以常法予以冷凍粉碎成20篩 目以下的粉末。將0.3克之以130°C真空乾燥該粉末12小 時之物，置入內徑約爲8毫米、長度爲140毫米之玻璃試 驗管中，以70°C真空乾燥12小時後，將塡入矽膠之乾燥 -94- 1276646 五、發明說明（93) 管接續於該試驗管上部，在乾燥之空氣下，浸漬在230°C 之鹽浴中加熱1 5分鐘。與上述TS同樣地使用下述計算式 ，從加熱試驗後PET之IV求得TS。惟，係分別指[IV] i及 [IV]n加熱試驗前和加熱試驗後之IV (dl/克）。 冷凍粉碎係使用硏磨機（美國斯佩克斯公司製6750型） 來進行。將約2克之樹脂薄片與專用的衝擊器裝入專用胞 室後，將胞室設定在裝置上、充塡液態氮至裝置內，保持 約10分鐘；之後，以速率10 (衝擊器爲1秒鐘約20次左 右後）進行粉碎約5分鐘。 TOS = 0.245 { [IVhl·1.47 - [IV]，1.47} (1 0 )薄膜之熱安定性 (i)薄膜之製膜 將後述之實施例及比較例中以熔融聚合所得到的PET薄 片，於135°C下予以真空乾燥6小時。之後，供給至押出 機，以280°C、片狀熔融押出，於表面溫度保持20°C之金 屬輥上急冷固化，而得到厚度爲1400微米之鑄膜。 接著，以加熱輥組及紫外線加熱器、100°C加熱該鑄膜 ，之後，利用具周速差之輥組，縱方向上之設定値爲3 . 5 倍拉伸，而得到單軸定向PET膜。接著，繼續溫和地於 1 20°C、以寬度方向上之設定値爲4.0倍拉伸之，於寬度 長爲固定狀態、260°C下’利用紅外線加熱器加熱0.5秒 鐘，進一步以200°C進行3%驰緩處理23秒鐘，而得到100 微米之雙軸定向之PET膜。 -95- 1276646 五、發明說明（94) (ii) 以回收九粒得到薄膜之製膜 將利用上述（i)記載的方法所得到的PET膜裁斷成短柵 狀，真空乾燥後予以投入押出機，將在溫度設定爲280°C 下熔融的樹脂，從直徑爲5毫米之噴嘴押出後，以水冷卻 、予以切斷而得到回收九粒。 將利用熔融聚合所得到之PET樹脂薄片、與前述回收之 九粒，以50 : 50之重量比混合之，在135°C下真空乾燥6 小時。之後，供給至押出機，以280°C、片狀熔融押出， 於表面溫度保持20°C之金屬輥上急冷固化，而得到厚度爲 1400微米之鑄膜。 接著，以加熱輥組及紫外線加熱器、100 °C加熱該鑄膜 ，之後，利用具周速差之輥組，縱方向上之設定値爲3.5 倍拉伸，而得到單軸定向PET膜。接著，繼續溫和地於 1 20°C、以寬度方向上之設定値爲4.0倍拉伸之，而得到 100微米之雙軸定向之PET膜。 將所得到薄膜再度裁斷成短柵狀，以上述同樣的做法得 到之回收九粒來進行薄膜之製膜。反行進行本操作5次以 上。 (iii) 薄膜熱安定性之評量 將所得到的薄膜切出長度爲8公分、寬度爲4公分之試 驗片，慢慢地將所得到的薄膜之長度方向予以拉伸，以評 量切割容易度。〇：良好；X:不良。 (11 )薄膜之耐熱老化性 -96- 1276646 五、發明說明（95) 將利用上述（10)(i)之方法所得到的薄膜，予以切出長 度爲10公分、寬度爲5公分之試驗片，使用齒輪式熱風 乾燥機、以200°C將試驗片予以處理100小時後，慢慢地 將所得到的薄膜之長度方向予以拉伸，以評量薄膜之耐熱 老化性。〇：良好；X :不良。 (12) 合成磷化合物之1H-NMR測定 將化合物溶解在CDC13或d6-DMSO中，於室溫下，使用 法萊恩GEMINI -200測定之。 (13) 合成磷化合物之熔點測定 將化合物覆蓋在玻璃上，使用楊納可微熔點儀，以1 °C / 分鐘之昇溫速度測定之。 (14) 合成磷化合物之元素分析 磷之分析係將PET薄片予以溼式分解後，藉鉬藍-比色 法來進行。其他的金屬係使灰化/酸溶解後，利用高步率 電漿發光分析及原子吸光分析來進行。 (實施例1-1) (磷化合物之合成例） 以下述式（化44)所代表之磷化合物（磷化合物A)之合成 [化 4 4](In the formula (43), R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. R4 represents hydrogen and has a carbon number of 1 to 50. a hydrocarbon group, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group of 1 to 50. The 1 system represents an integer of 1 or more; m represents an integer of 1 or more; 1 + m is 3. The hydrocarbon group may also contain An alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group.) Examples of the above R3 may, for example, be hydrogen, a methyl group, an ethyl group, a propyl group, or the like. Isopropyl, η-butyl, t-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthyl, represented by _CH2CH2〇H . It can be used as, for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc., which can be used as a specific phosphorus compound of the present invention, for example, for example, Is an aluminum salt of ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, an aluminum salt of methyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate , aluminum salt of 3,5-di-t-butyl- 4-hydroxybenzylphosphonic acid isopropyl ester, aluminum of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid phenyl ester Salt, aluminum salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, and the like. Among them, it is preferably 3,5-di-tertiary-butyl-4-hydroxybenzylphosphonic acid-78-1276646. 5. Description of invention (77) Aluminum salt of ethyl ester, 3,5-di-third- The aluminum of the methyl ester of butyl-4-hydroxybenzylphosphonate is used in the case of using an alkali metal, an alkaline earth metal or an aluminum salt in the above phosphorus compound, and the amount thereof is added, that is, the aluminum atom in the finally obtained polyester. The content of the phosphorus atom must be within the scope of the patent application of the present invention. By this method, it is possible to suppress the effect of occurrence of foreign matter insoluble in polyester, and to improve the problem of clogging of the yarn during spinning or forming. The antimony compound which can be used in the polymerization catalyst of the present invention is, for example, antimony trioxide, antimony pentoxide, antimony acetate, antimony oxide or the like. The special system uses antimony trioxide. Further, it can be used as a bismuth compound, and examples thereof include cerium oxide and cerium tetrachloride. The special system uses cerium oxide. Cerium dioxide can be used in both crystalline and amorphous forms. Further, other polymerization catalysts such as a titanium compound and a tin compound may be used as the titanium compound, and examples thereof include tetra-11-propyl titanium, tetraisopropyl titanium, and tetra-n-butyl titanium. Tetraisobutyl titanium, tetra-t-butyl titanium, tetracyclohexyl titanium, tetraphenyl titanium, tetrabenzyl titanium, lithium oxalate titanate, potassium oxalate titanate, manganese oxalate titanate, titanium oxide, titanium and tantalum a composite oxide of chromium, an alkali metal or an alkaline earth metal, a normal ester of titanium or a condensed orthoester, a normal ester of titanium or a reaction product of a condensed orthoester and a hydroxycarboxylic acid, a normal ester of titanium or a condensed orthoester A reaction product formed from a reaction product of a hydroxycarboxylic acid and a phosphorus compound, a normal ester of titanium or a condensed normal ester, and a polyol having at least two hydroxyl groups, and a 2-hydroxycarboxylic acid and a salt group. Among them, it is preferably a composite oxide of titanium and ruthenium, a composite oxide of titanium and manganese, a normal ester of titanium or a condensed orthoester and a hydroxycarboxylic acid-79-1276646, a description of the invention (78) and a phosphorus compound. Reaction product. Further, as the tin compound, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, single Butyl hydroxytin oxide, triisobutyl tin oxide, diphenyl tin laurate, monobutyl tin trichloride, dibutyl tin sulfide, dibutyl hydroxy tin oxide, methyl stannic acid, ethyl stannic acid, etc. . Particularly preferred is the use of monobutyl hydroxy tin oxide. The cobalt compound which may be added in the present invention is not particularly limited to a certain substance, but specific examples thereof are, for example, cobalt acetate, cobalt nitrate, cobalt chloride, ethyl ruthenium acetate, cobalt naphthalate. And its hydrates, etc. Preferably, it is a cobalt acetate tetrahydrate. According to the method of the present invention, in the production of a polyester, it is preferred to add a phenolic compound to increase the thermal stability of the polyester. The phenol compound which can be used in the present invention is not particularly limited to a compound having a phenol structure, and for example, is 2,6-di-tert-butyl-4-methylphenol, 2,6. -di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-methylphenol, 2,6-di- Third-pentyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-di-cyclohexyl-4-n-octylphenol, 2 -isopropyl-4-methyl-6-tert-butylphenol, 2-tris-butyl-2-ethyl-6-tris-octylphenol, 2-isobutyl-4-ethyl -6-tris-hexylphenol, 2·cyclohexyl 4-n-butyl-6-isopropylphenol, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1, 3-tris(2-methyl-4-hydroxy-5th-butenyl)ethane, triethylene glycol-tris[3-(3-tri-butyl-5-methyl--80- 1276646 V. INSTRUCTION DESCRIPTION (79) 4-Hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl) Propionate], 2,2-thiodiethylidene [3-(3,5-di-tri-butyl-4,4-hydroxyphenyl)propionate], N,N'- Hexamethylene bis(3,5-di-t-butyl-4 -hydroxy-hydrocinnamic acid, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tri-butyl)isocyanate, 1,3,5-tris(3,5-di -T-butyl-4-hydroxyphenyl)isocyanate, 1,3,5-tris[3,5-di-tris-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanate, Tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanate, 2,4-bis(η-octylthio)-6-(4-hydroxy-3, 5 -di-t-butylanilino)isocyanate, 1,3,5-trin, tetrakis[methylene(3,5-di-tri-butyl-4-hydroxy)hydrocinnamate]amine, Bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyric acid diol]ether, N,N,bis[3-(3,5-di-tertiary-butyl- 4-hydroxyphenyl)propanyl]cultivated, 2,2'-oxazolamide II [ethyl-3-(3,5-di-tris-butyl-4-hydroxyphenyl)propionate , bis[2-tri-butyl-4-methyl-6-(3-tri-butyl-5-methyl-2hydroxybenzyl)phenyl]p-nonanoate, 1,3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-di[1,1-dimethyl-2- {θ - (3-Terti-butyl-4-hydroxy-5-methylphenyl)propanyloxy}ethyl]-2,4,8 10-tetradecyl[5,5]undecane, 2,2-bis[4-(2-(3,5-di-tris-butyl-4-hydroxypropylanilinyloxy))ethoxybenzene Base] propyl, no-(3,5---di-di-butyl-4-phenyl) propionic acid ester, tetra-[methyl-3-(3,,5,-di-third -butyl-4-hydroxyphenyl)propionate]methane, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, ι,υ-three (2-methyl-4-hydroxy-5-tris-butylphenyl)butane, thiodiethylene-di-81 - 1276646 V. Description of the invention (8〇) [3-(3,5-two -T-butyl-4-hydroxyphenyl)propionate], ethyl bis(oxyethyl)di[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl) Propionate, trihexaol-di-[3-(3·-t-butyl-5-methylphenyl)propionate, 1,1,3-tris(2-methyl-4) -[3-(3,5-Di-Terti-butyl-4-hydroxyphenyl)propenyloxy]-5-tris-butylphenyl)butane. Here, it is also possible to use both at the same time. Among them, 1,3,5-trimethyl, 4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra-[methyl-3-( 3,5'-di-t-butyl-4-hydroxyphenyl)propionate]methane, thiodiethylene-bis[3-(3,5-di-tri-butyl-4) -Phenyl)propionate]. The phenol compound of the present invention is preferably a hindered phenol structure. The amount of the phenolic compound to be used in the present invention is preferably from 5 X 10·5 based on the number of moles of all constituent units of the carboxylic acid component such as a dicarboxylic acid or a polycarboxylic acid in the obtained polyester. Molar% to 1% by mole; more preferably in the range from 1 X 10_4 mol% to 0.5 mol%. When the polyester is produced in accordance with the present invention, it can be carried out by a method known per se. For example, in the case of producing PET, a method of esterifying and then re-condensing citric acid and ethylene glycol, or an alkyl ester of citric acid such as dimethyl phthalate, and ethylene glycol The method of performing the esterification exchange reaction and then re-condensing can be carried out by any of the methods. Further, the polymerization apparatus may be of a batch type or a continuous type. The catalyst used in the polymerization of the polyester according to the method of the present invention has catalytic activity not only for the esterification reaction of the polycondensation reaction but also for the esterification exchange. An alkyl ester of a dicarboxylic acid such as dimethyl phthalate, -82-1276646 5. Description of the invention (81) An esterification exchange reaction with ethylene glycol is usually carried out in the presence of an ester exchange catalyst such as zinc. However, it is also possible to use the catalyst of the present invention instead of the catalyst or to coexist with the catalyst. Further, the catalyst used in the polymerization of the polyester according to the method of the present invention may be one which has a catalytic activity for melt polymerization, solid phase polymerization or solution polymerization, and may be produced by any method. The catalyst used in the polymerization of the polyester according to the method of the present invention can be added to the reaction system at any stage of the polymerization. For example, it may be added to the reaction system before the start of the esterification reaction or the esterification exchange reaction and at any stage in the middle of the reaction, or before the start of the polycondensation reaction and at any stage in the middle of the reaction. In particular, it is preferred to add an aluminum-free compound just before the start of the polycondensation reaction. The method of adding the catalyst or other compound used in the polymerization of the polyester according to the method of the present invention may be a slurry or a solution of a solvent such as a powder or a kneaded form or a glycol, and is not particularly limited. Further, a catalyst component and other compounds may be added in advance, and may be added separately. Further, a mixture of a catalyst solution of the aluminum compound of the present invention and a mixture of other compounds may be added and added separately. Further, the catalyst component and other compounds may be simultaneously added to the side polymerization system, and the individual components may be added separately. Further, the catalyst and other compounds may be added at once, and may be added in plural times. The term "polyester" as used in the present invention means at least one or more selected from the group consisting of ester-forming derivatives such as dicarboxylic acids and polycarboxylic acids, and the description of the invention is included in the description of the invention (II-83-1276646). 82) at least one or more selected from the group consisting of alcohol polyols; or a product derived from a hydroxycarboxylic acid and an ester-forming derivative thereof; or a product formed from a cyclic ester. It can be used as a dicarboxylic acid, for example, oxalic acid, malonic acid, crotonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and ten base. Dicarboxylic acid, dodecyl dicarboxylic acid, tetradecyl dicarboxylic acid, hexadecyl dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1, 2 a saturated aliphatic group of cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-n-decene dicarboxylic acid, a dimer acid, or the like a dicarboxylic acid or an ester-forming derivative thereof, an unsaturated aliphatic dicarboxylic acid exemplified as fumaric acid, maleic acid or itaconic acid or an ester-forming derivative thereof; o-decanoic acid, isodecanoic acid, or the like Citrate, 5-(alkali metal) thioisophthalic acid, diphenyl acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylthiodicarboxylic acid, 4,4, diphenyl ether dicarboxylic acid, 1 , 2-di(phenoloxy)ethane- ρ,ρ·-dicarboxylic acid, palmitic acid, stilbene dicarboxylic acid, and the like, an aromatic dicarboxylic acid or an ester-forming derivative thereof. Among these dicarboxylic acids, preferred are citric acid, naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid. It can be used as a polycarboxylic acid other than the dicarboxylic acid, for example, ethane tricarboxylic acid, propane tricarboxylic acid, butane tricarboxylic acid, pyromellitic acid, trimellitic acid, trihydroxyl Formic acid, 3,4,3,4'-biphenyl-p-citric acid, and ester-forming derivatives thereof. It can be used as a diol, for example, ethylene glycol, 1,2-propyl-84- 1276646, invention description (83) diol, 1,3-propanediol, diethylene glycol, triethyl Glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol , 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,1 〇-decethylene glycol, 1,12-dodecyl diol, polyethylene glycol, polytrimethylene An aliphatic diol exemplified by an alcohol, a polytrimethylene glycol or the like; hydroquinone, 4,4'-hydroxydiphenol, 1,4-bis(yS-hydroxyethoxy)benzene, 1,4-bis(quinone) -Hydroxyethoxyphenyl) maple, bis(p-hydroxyphenyl)ether, bis(P-phenyl) maple, bis(P-phenyl)carb, 1,2-bis(P-hydroxybenzene) An aromatic diol exemplified by ethane, biphenol A, biphenol C, 2,5-naphthalene diol, diol having ethylene oxide added thereto, etc.; In order to use ethylene glycol and 1,4-butyl The diol is ideal. It can be used as a polyol other than the diol, for example, hydroxymethylmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, hexanetriol, etc. . It can be used as a hydroxycarboxylic acid, for example, lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, P-(2-hydroxyethoxy)benzoic acid. And hydroxycyclohexanecarboxylic acid, or an ester-forming derivative thereof. The cyclic ester may, for example, be ε-caprolactone, $-propiolactone, /3_methyl_y3_propiolactone, valerolactone, glycolate, lactide, etc. The polyester of the present invention may be a copolymerized component in the form of a known phosphorus compound, -85-1276646, and the invention (84). The phosphorus compound is preferably a difunctional phosphorus compound, and examples thereof include, for example, dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyethyl)methylphosphinic acid, ( 2-carboxyethyl)phenylphosphinic acid, methyl (2-methoxycarboxyethyl)phenylphosphinate, methyl (4-methoxycarboxyethyl)phenylphosphinate, [2-( Ethylene glycol ester of /3-hydroxyethoxycarbonyl)ethyl]methylphosphinic acid, (1,2 ·dicarboxyethyl)methylphosphinium oxide, 9,10-dihydro-10-oxygen- (2,3-Carboxypropyl)-i〇-phosphine, phenethylamino-10 oxide, and the like. By making the copolymerization component containing these phosphorus-based compounds, the flame retardancy and the like of the obtained polyester can be increased. The ester-forming derivative of a polyvalent carboxylic acid or a hydroxycarboxylic acid may, for example, be a hospital ester, an acid chloride or an acid anhydride. In the polyester used in the present invention, it is preferred to use a main acid component as a phthalic acid or an ester-forming derivative thereof, or a naphthalene dicarboxylic acid or an ester-forming derivative thereof; the main alcohol component is a stretched alkane Alcohol polyester. Preferably, the polyester is based on the total acid component of citric acid or an ester-forming derivative thereof, or the entire acid component of the naphthalene dicarboxylic acid or an ester-forming derivative thereof, preferably containing citric acid. Or a polyester-forming derivative thereof and a polyester having a total amount of naphthalene dicarboxylic acid or an ester-forming derivative thereof of 70 mol% or more, more preferably a polyester of 8 mol% or more, most preferably More than 90% polyester. The main alcohol component is a polyester of alkylene glycol, preferably more than 70 mol% of the total amount of alkylene glycol, more preferably 80 mol, based on the total diol component. More than 100% of the polyester is most preferably a polyester of 90 mol% or more. The diol in the present invention may also be a ring structure in which a substituent or a lipid is contained in the molecular chain, which is a structure of the ring (85). As the naphthalene dicarboxylic acid or an ester-forming derivative thereof used in the present invention, for example, it is preferably 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1, A naphthalene dicarboxylic acid such as 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid or 2,7-naphthalene dicarboxylic acid or an ester-forming derivative thereof. The alkylene glycol which can be used in the present invention is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-butanediol. , 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2 - Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decethylene glycol, 1,12-dodecyl glycol, and the like. At the same time, two or more of these may be used in the polyester of the present invention, and may be used as an acid component other than a phthalic acid or an ester-forming derivative thereof or a naphthalene dicarboxylic acid or an ester-forming derivative thereof. Is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decacodicarboxylic acid, dodecyl dicarboxylic acid, Tetradedyldicarboxylic acid, hexadecyldicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3 a saturated aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-n-decene dicarboxylic acid or a dimer acid, or an ester-forming derivative thereof, An unsaturated aliphatic dicarboxylic acid or an ester-forming derivative thereof as exemplified by fumaric acid, maleic acid, itaconic acid, etc.; o-decanoic acid, isophthalic acid, p-nonanoic acid, 5-(alkali metal) sulfur Citrate, bis-87- 1276646 V. Description of invention (86) benzoic acid, 4,4,-diphenyldicarboxylic acid, 4,4'-diphenylthiodicarboxylic acid, 4,4,-diphenyl Ether dicarboxylic acid, I,2-di(phenoloxy)ethane-p,p,monodecanoic acid,palmitic acid An aromatic diterpene acid or an ester thereof exemplified by a hydrazine dicarboxylic acid or the like; an ethane tricarboxylic acid, a propane trisodium acid, a butyl triglyceride, pyromellitic acid, trimellitic acid, and triacetic acid , 3,4,3,,4'·biphenyl-antimonic acid' and its ester-forming derivatives; lactic acid, citric acid, malic acid, tartaric acid, trans-acetic acid, 3-butyric acid, p-trans Benzoic acid, P-(2-propionyloxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or an ester-forming derivative thereof. Further, 'the ring shape exemplified by ε-caprolactone, /3 -propiolactone, /3 -methyl-/3-propiolactone, 5-valerolactone, glycolate, lactide, etc. may be contained. Ester. In the polyester of the present invention, it can be used as a diol component other than an alkylene glycol, for example, containing diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetrazol. An aliphatic diol exemplified by methyl glycol or the like; hydroquinone, 4, 4, hydroxydiol, 1,4-bis(0-hydroxyethoxy)benzene, 1,4-bis(/3-hydroxyethoxy) Phenyl) maple, bis(indolyl-hydroxyphenyl) ether, bis(indolyl-hydroxyphenyl) maple, bis(indolyl-hydroxyphenyl)methane, 1,2 bis(ρ-hydroxyphenyl)ethane, An aromatic diol exemplified by biphenol A, biphenol C, 2,5-naphthalenediol, diol in which ethylene oxide is added to the diol, etc.; trimethylolethane, trishydroxymethyl A polyol exemplified by an alkane, trimethylolpropane, pentaerythritol, glycerin or hexanetriol is a copolymerization component. Further, in the polyester of the present invention, a known phosphorus-based compound may be included as a copolymerization component. The phosphorus-based compound is preferably a difunctional phosphorus-based compound, for example, dimethyl phenylphosphonate, phenylphosphonic acid 2.8- 1276646. 5. Description of the invention (87) phenyl ester, (2) -carboxyethyl)methylphosphinic acid, (2-carboxyethyl)phenylphosphinic acid, methyl (2-methoxycarboxyethyl)phenylphosphinate, (4-methoxycarboxyethyl) Methyl phenylphosphinate, ethylene glycol of [2-(/3-hydroxyethoxycarbonyl)ethyl]methylphosphinic acid, (1,2-dicarboxyethyl)methylphosphine oxide, 9, 10-Dihydro-10-oxo-(2,3-carboxypropyl)-10-phosphine phenylethenyl-10-oxide. By making the copolymerization component containing these phosphorus-based compounds, the flame retardancy and the like of the obtained polyester can be increased. It can be used as the polyester of the present invention, and is preferably polyethylene terephthalate, propylene terephthalate, poly(1,4-cyclohexanemethylene terephthalate), polynaphthoquinone. Ethylene glycol diester, polybutylene naphthalate, propylene glycol naphthalate and copolymers thereof; among them, polyethylene terephthalate and copolymers thereof are particularly preferred. In order to improve the dyeability in the case of using as the ester fiber, a preferred embodiment is a copolymerized component of a polycarboxylic acid having a calcium sulfate metal salt group as a constituent of the polyester of the present invention. . The compound containing a metal-containing sulfate group used as a copolymerization monomer is not particularly limited to a certain substance, and for example, is, for example, 5-sodium thioisodecanoate or 2-sodium sulphate versus citric acid. Salt, 5-lithium isothioate, 2-lithium sulphate, 5-potassium sulfonate, 2-potassium sulfonate, or a lower alkyl derivative thereof. In the present invention, it is particularly preferable to use 5-sodium thioisocyanate or an ester-forming derivative thereof. The amount of the copolymerization of the metal sulfate-containing compound is preferably from 0.3 to 10.0 mol%, more preferably from 0.80 to 5.0 mol%, based on the acid component constituting the polyester. When the amount of copolymerization is too small, the dyeability of the salt-based dye may be deteriorated, -89-1276646. 5. Description of the invention (88) When it is too much, in the case of making fibers, not only the silkiness will become Good, and thickening, so that the fiber strength obtained is not sufficient. Further, when it is copolymerized with a metal sulfate-containing compound of 2.0 mol% or more, the modified polyester fiber having a normal pressure dyeability can be imparted. Further, by selecting an appropriate dyeable monomer, the amount of the metal sulfate-containing compound to be used can be appropriately reduced. The dyeable monomer is not particularly limited to a certain substance, and for example, a long-chain diol compound represented by polyethylene glycol or polytetramethylene glycol, or adipic acid An aliphatic dicarboxylic acid represented by azelaic acid or sebacic acid. After the polyester is polymerized according to the method of the present invention, the catalyst is removed from the polyester, or the catalyst is deactivated by the addition of a phosphorus compound or the like, whereby the thermal stability of the polyester can be made higher. The polyester of the present invention may include an oxidation preventive agent such as a phenol type or an aromatic amine type. For example, if one or more of these may be contained, the thermal stability of the polyester may be changed. Got higher. In the polyester of the present invention, it may include a blue agent, an organic system, an inorganic system, or an organometallic dye, a pigment, a fluorescent whitening agent, etc.; and one or more of these may be contained. , it will be able to suppress the coloring of the yellow color of the polyester. The polyester of the present invention may also include other polymers or stabilizers, oxidation inhibitors, electricity generators, antifoaming agents, dyeability improvers, dyes, pigments, deodorants, and other additives. Such an additive may be added at the time of polymerizing the polyester or after the polymerization, or at any stage of the molding of the polyester (90), the invention (89); the more appropriate stage is due to the polymer The characteristics, or the performance requirements of the polyester molded body vary. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. The evaluation method used in the embodiment of the present invention is as follows. (1) The content of metals and phosphorus in the polymer. The contents of phosphorus, cerium and lanthanum are determined by a fluorescent X-ray method. The test sample polyester was placed in a ring of 5 mm, 40 mm diameter stainless steel placed on a photographic iron plate. It was melted by heating at 300 ° C for 10 minutes in an oven. After taking it out and cooling it, the sample formed by the loop was taken out, and the smooth side was measured. Further, another method is a chemical analysis method in which a plurality of points of a predetermined polyester are formed by the above method, and the intensity of the fluorescent X-rays is measured to obtain enthalpy and fluorescent X-rays obtained by chemical analysis. Check line. The content of phosphorus, strontium, and barium in each sample was calculated based on the calibration curve obtained by measuring the fluorescent X-ray intensity data of the sample polyester. The other metal content was measured by the following method. Weigh 1.0 g of polyester, ash it in a platinum carbide furnace at 550 ° C in a platinum crucible, cool to room temperature, and then make 6N hydrochloric acid (in the case of titanium is a mixture of hydrofluoric acid / hydrochloric acid) After dissolving, evaporating and solidifying, it was dissolved in 1.2 N hydrochloric acid, and supplied to a high-frequency plasma luminescence analysis (manufactured by Shimadzu Corporation, ICPS-2000) and atomic absorption spectrometry (manufactured by Shimadzu Corporation, AA-640-1 2). ) The sample on it. Further, in another method, a commercially available atomic absorption standard -91 - 1276646 5, invention description (9 〇) solution is used, and a concentration range of 1 to 30 mg/liter of each metal to be determined is determined. The calibration curve is used for high-frequency plasma luminescence analysis (Al, Ca, Mg, Co) and atomic absorption analysis (Na, Li, K) to make a calibration curve, which is based on the calibration curve. The metal content in the polyester was calculated from the analytical data of each sample. (2) Viscosity of polyester (IV) Dissolve 0.1 g of polyester in a mixed solvent of 25 ml of phenol/1,1,2,2-tetrachloroethane in a weight ratio of 6/4. Uberalda viscosity meter, measured at a temperature of 30 °C. (3) Sour acid The polyester was freeze-pulverized and dried under vacuum at 130 ° C for 12 hours or more. A 0.1 g sample was placed in the test, and 1 ml of benzyl alcohol was added to dissolve it. After dissolution, it was allowed to cool in a water bath. 10 ml of a chloroform, phenolphthalein indicator was added, and a 0.1 N NaOH methanol/benzyl alcohol = 1/9 solution was used for titration, and then acid hydrazide was obtained. (4) Diethylene glycol content (DEG) 0.1 g of the polymer was dissolved in 2 ml of methanol, and decomposed by heating at 250 ° C, and then quantified by gas chromatography (using GC-14B manufactured by Shima Seiki Co., Ltd.). Seek. The analytical column was filled with a PEG-ΗΤ column packed with Diyru Scientific. (5) Differential scanning calorimetry (DSC) was measured using a DSC2920 manufactured by Sigma Instruments. Sealing about 10.0 mg of polyester in a special aluminum basin for automatic sampler manufactured by ΤΑ Instruments Co., Ltd. -92-1276646. 5. Inventive (91), heating to 280 °C at a heating rate of 50 °C/min. After reaching 280 ° C for 1 minute, it was quenched with liquid nitrogen. Thereafter, the temperature was raised to 300 °C at a temperature increase rate of 20 ° C /min from room temperature to obtain a crystallization temperature Tel and a melting point Tm at the time of temperature rise. After 2 minutes from reaching 300 ° C, the temperature was lowered at 10 ° C /min to determine the crystal temperature Tc2 at the time of temperature drop. The maximum part of each peak is used as the temperature of Tel, Tm, and Tc2. (6) Hue The color difference meter (TC- 1 500MC-88 type, manufactured by Toshiro Denshoku Co., Ltd.) was used to measure L値, a値, b値 of Hunter's characteristic. In the case where the measurement sample is a polyester resin sheet, a sheet having a diameter of about 2 mm and a length of about 3 mm is obtained by the method described in the examples, and air-dried on a filter paper at room temperature for about one day and night, and then used for measurement. Chroma. (7) Evaluation of the bottle pressure at the time of spinning and the breaking at the time of stretching. The PET resin sheet obtained by melt polymerization is dried and then supplied to a melt extruder, using a 20 micron filter from 290°. A spun of a total of 108 orifices having a pore diameter of 0.14 mm Φ was spouted, and it was cooled by a usual method. After refueling, it was taken at 1,720 m/min. The drawing was continued to preheat the roll at 80 ° C, the set temperature was 150 ° C, and the stretching was 2.127 times, and a polyester drawn yarn of 47 d t ex and 168 filament was obtained. Further, the evaluations of Examples 1 to 5 were carried out using different spinning machines. According to the degree of increase in filtration pressure at the time of spinning, it is evaluated as follows. 〇: I really can't recognize the increase in filtration pressure. -93- I276646 V. Inventive Note (92) △: The increase in filtration pressure can be recognized; X: The filtration pressure rises remarkably. According to the breaking frequency at the time of stretching, it is evaluated as follows. 〇: It does not cause broken wire; △: It causes broken wire; X: Multiple broken wires occur. (8) Thermal stability parameter (TS) 1 g of the melt polymerization IV is 0.64 to 0.66 dl / g (pre-melting test: [IVh) PET resin sheet, placed in a glass test tube with an inner diameter of about 14 mm After drying at 130 ° C for 12 hours in vacuum, the glass test tube on the vacuum line was depressurized, and nitrogen gas was sealed for 5 times or more, and then sealed with nitrogen gas at 100 Torr. The test tube was immersed in a salt bath at 300 ° C, and after being kept in a molten state for 2 hours, the sample was taken out, freeze-pulverized, and vacuum dried, and then IV (pre-melting test: [IV] f) was measured. The TS was obtained from the [IV]f using the following calculation formula. This type is cited (Shangshan La: Japan Rubber Association, Vol. 63, No. 8, page 497, 990). TS = 0.245 { [IVV1.47 - [IV],.47 } (9) Thermal Oxidation Stability Parameter (TOS) The melt polymerization IV is 0.64~0.66 dl/g (pre-melting test: [IVh) PET resin The sheet is frozen and pulverized into a powder of 20 mesh or less by a usual method. 0.3 g of the powder was vacuum dried at 130 ° C for 12 hours, placed in a glass test tube having an inner diameter of about 8 mm and a length of 140 mm, and dried under vacuum at 70 ° C for 12 hours, and then poured into a silicone rubber. Drying -94- 1276646 V. INSTRUCTIONS (93) The tube is connected to the upper part of the test tube and immersed in a salt bath at 230 ° C for 15 minutes under dry air. The following calculation formula was used in the same manner as the above TS, and TS was determined from the IV of PET after the heating test. However, they refer to [IV] i and [IV]n before heating test and IV after heating test (dl/g). The freeze pulverization was carried out using a honing machine (Model 6750, manufactured by Specex, USA). After loading about 2 grams of the resin sheet and the special impactor into the dedicated cell, the cell is set on the device, filled with liquid nitrogen into the device for about 10 minutes; then, at a rate of 10 (the impactor is 1 second). After about 20 times, the pulverization was carried out for about 5 minutes. TOS = 0.245 { [IVhl·1.47 - [IV], 1.47} (1 0 ) Thermal stability of film (i) Film formation of film The PET sheet obtained by melt polymerization in the examples and comparative examples described later was It was vacuum dried at 135 ° C for 6 hours. Thereafter, the film was supplied to an extruder, melted at a sheet temperature of 280 ° C, and rapidly solidified on a metal roll having a surface temperature of 20 ° C to obtain a cast film having a thickness of 1400 μm. Next, the cast film was heated at 100 ° C with a heating roller set and an ultraviolet heater, and then a uniaxially oriented PET was obtained by using a roll set having a circumferential speed difference and setting the 値 in the longitudinal direction to 3.5 times. membrane. Then, continue to gently stretch at a temperature of 1200 ° C at a setting of 4.0 in the width direction, and at a constant width of 260 ° C, 'heated by an infrared heater for 0.5 second, further 200 ° C was subjected to a 3% relaxation treatment for 23 seconds to obtain a 100 micrometer biaxially oriented PET film. -95- 1276646 V. INSTRUCTION OF THE INVENTION (94) (ii) The film obtained by recovering nine films is cut into a short grid shape by the method described in the above (i), vacuum-dried, and then placed in a extruder. The resin melted at a temperature of 280 ° C was extruded from a nozzle having a diameter of 5 mm, and then cooled with water and cut to obtain nine particles. The PET resin sheet obtained by melt polymerization and the above-mentioned nine recovered particles were mixed at a weight ratio of 50:50, and vacuum-dried at 135 ° C for 6 hours. Thereafter, the film was supplied to an extruder, melted at a sheet temperature of 280 ° C, and solidified on a metal roll having a surface temperature of 20 ° C to obtain a cast film having a thickness of 1400 μm. Subsequently, the cast film was heated at 100 ° C by a heating roll group and an ultraviolet heater, and then a uniaxially oriented PET film was obtained by using a roll set having a peripheral speed difference and setting the 値 in the longitudinal direction to 3.5 times. Subsequently, it was further gently stretched at 1200 ° C in a width direction of 4.0 to obtain a 100 μm biaxially oriented PET film. The obtained film was again cut into a short grid shape, and nine films were recovered in the same manner as described above to form a film for film formation. Perform this operation more than 5 times in reverse. (iii) Evaluation of thermal stability of the film The obtained film was cut into a test piece having a length of 8 cm and a width of 4 cm, and the length of the obtained film was slowly stretched to evaluate the cutting speed. degree. 〇: Good; X: Bad. (11) Heat aging resistance of film-96- 1276646 V. Description of the invention (95) A test piece obtained by the method of the above (10) (i) was cut out to have a length of 10 cm and a width of 5 cm. The test piece was treated at 200 ° C for 100 hours using a gear type hot air dryer, and then the longitudinal direction of the obtained film was gradually stretched to evaluate the heat aging resistance of the film. 〇: Good; X: Bad. (12) 1H-NMR measurement of synthetic phosphorus compound The compound was dissolved in CDC13 or d6-DMSO, and measured at room temperature using a Fahrenheit GEMINI-200. (13) Determination of the melting point of the synthetic phosphorus compound The compound was coated on a glass and measured at a temperature rising rate of 1 ° C /min using a Younger Micro melting point apparatus. (14) Elemental analysis of synthetic phosphorus compounds Phosphorus analysis was carried out by wet-decomposing PET flakes by a molybdenum blue-colorimetric method. Other metals are dissolved by ashing/acid, and then subjected to high-step plasma luminescence analysis and atomic absorption analysis. (Example 1-1) (Synthesis Example of Phosphorus Compound) Synthesis of a phosphorus compound (phosphorus compound A) represented by the following formula (Chem. 44) [Chem. 4 4]
-97- 1276646 五、發明說明（96) 鈉（0 -乙基3, 5 -二-第三-丁基-4-羥苯基膦酸酯）之合成 在6.5克（84毫莫耳）50%氫氧化鈉和6.1毫升甲醇之混 合溶液中加入5克（14毫莫耳）之二乙基（3, 5 -二-第三-丁 基-4_羥基）膦酸酯（Iragnoxl 222，汽巴·特殊化學品公 司製）之甲醇溶液，於氮氣氛圍氣下，進行迴流加熱24小 時。反應後，一邊冷卻反應混合物，一邊加入7.33克（70 毫莫耳）之濃鹽酸，取出析出以異丙醇予以洗淨後，減壓 餾除過濾液。將所得到的殘渣溶解在熱異丙醇中，取出不 溶分，減壓餾除異丙醇後，以熱庚烷洗淨殘渣，乾燥之而 得到3.4克（69%)之鈉（0-乙基3,5-二-第三-丁基-4-羥 基膦酸酯）。 形狀：白色粉末； 熔點：294〜302°C (分解） lH-NMR(d6-DMSO, δ): 1.078(3H, t, J=7Hz), 1.354 (18H, s), 2.71K2H, d), 3 ·724(2Η. m· J=7Hz)，6·626(1Η, s),, 6.9665(2H, s) 元素分析（括弧內爲理論値）：Na : 6·36%(6·56%)、P : 9.18%(8.84%) 0 -乙基3, 5 -二-第三-丁基-4-羥 基膦酸（磷化合Α)之 合成 在室溫攪拌下，於20毫升之含1克（2.8毫莫耳）鈉（0- 乙基3, 5 -二-第四-丁基-4-羥苯基膦酸鹽）的水溶液中加入 1 .5克濃鹽酸，攪拌1小時。將150毫升的水加入反應混 合物中，濾取、水洗、並乾燥所析出之結晶，而得到8 2 6 毫克（88%)之〇-乙基3,5-二-第三-丁基-4-羥基膦酸。 -98- 1276646 五、發明說明（97) 形狀：板狀結晶； 熔點：126〜127°C • · · - * β-NMR (CDC13，5):1·207(3Η，t，J=7Hz), 1·436(18Η，s)，·3·013(2Η, d), 3.88 8 (2H, m，J=7Hz)，7.088(2H, s), 7.679-8,275(lH, br). (聚酯聚合例） 使用2升之附有攪拌機的不銹鋼製高壓釜，對依照常法 從高純度的對酞酸與乙二醇製造得到之雙（2 -羥乙基）對酞 酸酯和寡聚物之混合物，加入2 . 5克/升之三乙醯乙酸鋁 的乙二醇溶液、及20克/升之上述磷化合物A的乙二醇溶 液、以及50克/升之醋酸鈉的乙二醇溶液所做成之聚縮合 觸媒。於該化合物最終所得到之聚合物中各金屬原子及磷 原子之含量，係依照表1所示之量添加。經添加的觸媒中 金屬成分之投入量，至少是與依照聚合中、成形中揮散的 分析結果所得到的數値相同，但所添加的磷成分則是多於 聚合中、成形中揮散的分析結果。又，添加量係因應在聚 合中所使用的反應器之特性、及聚合條件而適當地選定。 上述溶液經添加後，於氮氛圍氣、常壓、245 °C下，攪拌 10分鐘。接著，花50分鐘昇溫至275°C爲止，慢慢地將 反應系壓力下降爲0 . 1托利，進一步在275°C、0 . 1托利 進行聚縮合反應。將聚對酞酸乙二酯到達0.65 dl/克所需 要的聚合時間示於表1中。又，依照常法將在上述之聚縮 合中所得到之IV爲0.65 dl/克的聚對酞酸乙二酯予以薄 片化。也就是說，在熔融聚合到達預定攪拌扭矩之時點， 導入氮氣至高壓釜中，回復至常壓，停止聚縮合反應後， -99- 1276646 五、發明說明（98) 於約0 . 1 Mpa加壓下，連續地以反應罐下部之吐出噴嘴 ，將熔融之聚合物押出成束狀，在冷水中急冷，以切割刀 切割成長爲約3毫米、直徑爲約2毫米之圓柱狀薄片。於 冷水中之保持時間爲約20秒鐘。使用該薄片來測定pet 之物性。結果，IV爲〇·65 dl/克，酸値爲2當量/噸， DEG 爲 2.1 莫耳 ％，Tm 爲 256.6°C，Tel 爲 166.0°C，Tc2 爲 188.6°C。又，L 値爲 66.0，a 値爲-1·8，b 値爲 3.6。 使用此種PET樹脂薄片來進行紡絲時之濾壓上昇、以及 拉伸時之斷絲之評量。評量結果係示於表1中。 (實施例1-2〜1-3、比較例1-1) 除了變更觸媒以外，以和實施例1 -1同樣的做法來聚合 聚酯。在各實施例及比較例中，使用來做爲觸媒之化合物 係分別示於表1。在該化合物最終所得到的聚合物中之各 金屬原子及磷原子之含量，係按照表1所示之量來添加。 各實施例及比較例之聚合結果、與紡絲時之濾壓上昇、以 及拉伸時之斷絲之評量結果係示於表1中。Iragnox 1425 係使用汽巴•特殊化學品公司製之物，而磷化合物A係使 用以和實施例1 -1同樣的方法合成之物。 [表1] 由上述之實施例和比較例可明白：當聚酯中金屬之含量 乃在本發明申請專利範圍內之物時，其紡絲和拉伸之作業 性係均優異；相對的，在本發明之申請專利範圍之外者， 結果當紡絲時會引起濾壓顯著地上昇、拉伸時也常發生斷 -100- 1276646 五、發明說明（99) 絲，其作業性係屬不良。 (實施例2-1) 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2-羥乙基）對酞酸酯和寡聚物之混合物，加入2.5克/升 之三乙醯乙酸鋁的乙二醇溶液、以及50克/升之醋酸鋰二 水合物的乙二醇溶液所做成之聚縮合觸媒。於該化合物最 終所得到之聚合物中各金屬原子及磷原子之含量，係依照 表2所示之量添加。但是，含有量係爲相對於聚合物中酸 成分之金屬原子，以莫耳％表示之。添加量係因應在聚合 中所使用的反應器之特性、及聚合條件而適當地選定。上 述溶液經添加後，於氮氛圍氣、常壓、245°C下，攪拌10 分鐘。接著，花50分鐘昇溫至275°C爲止，慢慢地將反應 系壓力下降爲0.1托利，進一步在27 5 °C、0.1托利進行 聚縮合反應。將聚對酞酸乙二酯到達0.65 dl/克所需要的 聚合時間示於表2中。又，依照常法將在上述之聚縮合中 所得到之IV爲0.65 dl/克的聚對酞酸乙二酯予以薄片化 。使用此種PET樹脂薄片來進行紡絲時之濾壓上昇、以及 拉伸時之斷絲之評量。評量結果係示於表2中。 (實施例2-2〜2-6、比較例2-1〜2-2) 除了變更觸媒以外，以和實施例2 -1同樣的做法來聚合 聚酯。.將結果示於表2。在實施例2 - 6中，除添加乙酸鎂 和乙酸鋁以做爲聚縮合觸媒，並添加相對於聚合物中之酸 成分計爲0,01莫耳％之苯基磺酸二甲酯。 -101- 1276646 五、發明說明（1〇〇) [表2] 由上述之實施例和比較例可明白：當聚酯中金屬之含量 乃在本發明申請專利範圍內之物時，其紡絲和拉伸之作業 性係均優異；相對的，在本發明之申請專利範圍之外者， 當紡絲時會引起濾壓顯著地上昇、拉伸時也常發生斷絲， 其作業性不佳。 (實施例3-1) 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2-羥乙基）對酞酸酯和寡聚物之混合物，加入2.5克/升 之三乙醯乙酸鋁的乙二醇溶液、及10克/升之Iragnox 1 425 (汽巴•特殊化學品公司製）的乙二醇溶液所做成之 聚縮合觸媒。於該化合物最終所得到之聚合物中各金屬原 子及磷原子之含量，係依照表3所示之量添加。添加量係 因應在聚合中所使用的反應器之特性、及聚合條件而適當 地選定。上述溶液經添加後，於氮氛圍氣、常壓、245 °C 下，攪拌10分鐘。接著，花50分鐘昇溫至275°C爲止， 慢慢地將反應系壓力下降爲0.1托利，進一步在275 °C、 〇 . 1托利進行聚縮合反應。將聚對酞酸乙二酯到達 0.65 dl/克所需要的聚合時間示於表3中。又，依照常法 將在上述之聚縮合中所得到之IV爲0.65 dl/克的聚對酞 酸乙二酯予以薄片化。使用該薄片來測定PET之物性。結 果，IV爲0.65 dl/克，酸値爲6當量/噸，DEG爲2.1莫 耳％，Tm 爲 256.3°C，Tc2 爲 186.2°C。又，L 値爲 68_9， -102- 1276646 五、發明說明（1〇1 ) a 値爲-2.56，b 値爲 5.49。 使用此種PET樹脂薄片來進行紡絲時之濾壓上昇、以及 拉伸時之斷絲之評量。評量結果係示於表3中。 (實施例3 - 2〜3 - 9、比較例3 -1〜3 - 3 ) 除了變更觸媒以外，以和實施例3-1同樣的做法來聚合 聚酯。在各實施例及比較例中，使用來做爲觸媒之化合物 係分別示於表3。在該化合物最終所得到的聚合物中之各 金屬原子及磷原子之含量，係按照表3所示之量來添加。 添加量係因應在聚合中所使用的反應器之特性、及聚合條 件而適當地選定。實施例3 - 9中，係倂用三氧化銻來做爲 觸媒。三氧化銻係依照使最終所得到的聚合物中銻原子含 量來添加。各實施例及比較例之聚合結果、與紡絲時之濾 壓上昇、以及拉伸時之斷絲之評量結果係示於表3中。 Iragnox 1425係使用汽巴•特殊化學品公司製之物，而 磷化合物A係使用上述之方法合成之物。 [表3] 由上述之實施例和比較例可明白：當聚酯中金屬之含量 乃在本發明申請專利範圍內之物時，其紡絲和拉伸之作業 性係均優異；相對的，在本發明之申請專利範圍之外者， 結果當紡絲時會引起濾壓顯著地上昇、拉伸時也常發生斷 絲，其作業性係屬不良。 (實施例4-1) 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 -103- 1276646 五、發明說明（1〇2) (2-羥乙基）對酞酸酯和寡聚物之混合物，加入13克/升之 三氯化鋁的乙二醇溶液、相對於聚酯之酸成分計鋁原子爲 0.014莫耳％、及10克/升之Iragnox 1425 (汽巴•特殊 化學品公司製）的乙二醇溶液、相對於聚酯之酸成分計 Iragnox 1425爲0.022莫耳％所做成之聚縮合觸媒，於氮 氛圍氣、常壓、245°C下，攪拌10分鐘。接著，花50分 鐘昇溫至27 5 °C爲止，慢慢地將反應系壓力下降爲0.1托 利，進一步在27 5 °C、0.1托利進行聚縮合反應。將聚對 酞酸乙二酯到達0.65 dl/克所需要的聚合時間示於表4中 。PET樹脂薄片中所含的鈣原子爲45 ppm，從而金屬原子 之總含量爲65 ppm。使用此種PET樹脂薄片來進行紡絲時 之濾壓上昇、以及拉伸時之斷絲之評量。評量結果係示於 表4中。 (實施例4-2) (磷化合物之合成例） 以下述式（2 1 )代表之磷化合物（NMPA )之合成 氮氣氛圍氣下，使8.31克（50毫莫耳）之亞磷酸三乙酯 、與8.83克（50毫莫耳）之1-氯化甲基酞之混合物產生氣 體（C2H5C1 )，終了以200°C (外溫）加熱約30分鐘。冷卻至 室溫後，得到10.38克（粗收率爲75%)之無色油狀液體。 ^-NMR (CDCls； 5)：1.151 (6H, t), 3.64K2H； d),' 3.948(4H. m), 7.381-7.579(4 H, m). 7.749-7.867(2H, m), 8.088-8.133(1H, m). (聚酯聚合例） 除了變更觸媒以外，以和實施例4-1同樣的做法來聚合 -104- !276646 五、發明說明（103) 聚酯。在本實施例中，係使用2 · 5克/升之三乙醯乙酸鋁 的乙二醇溶液、相對於聚酯之酸成分計鋁原子爲〇 · 〇 1 4莫 耳％、相對於聚酯之酸成分計爲0.014莫耳％之50克/升之 上述NMPA的乙二醇溶液、及0.02莫耳％之換算成聚酯爲 0.1重量％之Iragnox 1 330 (汽巴•特殊化學品公司製）的 乙二醇溶液、50克/升之乙酸鋰二水合物的乙二醇溶液、 相對於聚酯之酸成分計鋰原子爲〇.〇1莫耳％之化合物來做 爲聚縮合觸媒。 將聚對酞酸乙二酯到達0.65 dl/克所需要的聚合時間， 測定所得到PET樹脂薄片中所含之鋁原子量、和磷原子量 之結果，以及相對於磷原子之鋁原子比値示於表4中。 PET樹脂薄片中所含之鋰原子量爲4 ppm，從而金屬原子 之總含量爲24 ppm。使用此種PET樹脂薄片來進行紡絲時 之濾壓上昇、以及拉伸時之斷絲之評量。評量結果係示於 表4中。 (比較例4 -1 ) 除了變更觸媒以外，以和實施例4 -1同樣的做法來聚合 聚酯。使用1 3克/升之氯化鋁的乙二醇溶液、相對於聚酯 之酸成分計鋁原子爲0.015莫耳％、50克/升之乙酸鋰二水 合物的乙二醇溶液、相對於聚酯之酸成分計鋰原子爲0.06 莫耳％之化合物來做爲聚縮合觸媒。 將聚對酞酸乙二酯到達0.65 dl/克所需要的聚合時間示 於表4中。使用此種PET樹脂薄片來進行紡絲時之濾壓上 -105- 1276646 五、發明說明（1〇4) 昇、以及拉伸時之斷絲之評量。評量結果係示於表4中。 [表4] 由上述之實施例和比較例可明白：使用鋁化合物、磷化 合物、及苯酚系化合物所聚合之聚酯，當聚酯中金屬之含 量乃在本發明申請專利範圍內之物時，其紡絲和拉伸之作 業性係均優異。一方面，不使用磷化合物、及苯酚系化合 物者，其熱氧化安定性變差，同時紡絲時會引起濾壓顯著 地上昇、拉伸時也常發生斷絲，結果作業性不佳。 (實施例5-1) 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2-羥乙基）對酞酸酯和寡聚物之混合物，加入2.5克/升 之三乙醯乙酸鋁的乙二醇溶液、及10克/升之上述磷化合 物A的乙二醇溶液所做成之聚縮合觸媒。於該化合物最終 所得到之聚合物中各金屬原子及磷原子之含量，係依照表 5所示之量添加。添加量係因應在聚合中所使用的反應器 之特性、及聚合條件而適當地選定。上述溶液經添加後， 於氮氛圍氣、常壓、245t下，攪拌10分鐘。接著，花50 分鐘昇溫至275°C爲止，慢慢地將反應系壓力下降爲0.1 托利，進一步在27 5°C、0.1托利進行聚縮合反應。將聚 對酞酸乙二酯到達0.65 dl/克所需要的聚合時間示於表1 中。又，依照常法將在上述之聚縮合中所得到之IV爲 0.65 dl/克的聚對酞酸乙二酯予以薄片化。使用該薄片來 測定PET之物性。評量結果示於表5中。 -106- 1276646 五、發明說明（105) (實施例5-2) 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2-羥乙基）對酞酸醅和寡聚物之混合物，加入2.5克/升 之三乙醯乙酸鋁的乙二醇溶液、及10克/升之Iragnox 1425 (汽巴•特殊化學品公司製）的乙二醇溶液所做成之 聚縮合觸媒。於該化合物最終所得到之聚合物中各金屬原 子及磷原子之含量，係依照表5所示之量添加。添加量係 因應在聚合中所使用的反應器之特性、及聚合條件而適當 地選定。上述溶液經添加後，於氮氛圍氣、常壓、245 °C 下，攪拌10分鐘。接著，花50分鐘昇溫至275°C爲止， 慢慢地將反應系壓力下降爲0.1托利，進一步在275°C、 〇 · 1托利進行聚縮合反應。將聚對酞酸乙二酯到達 0.65 dl/克所需要的聚合時間示於表1中。又，依照常法 將在上述之聚縮合中所得到之IV爲0.65 dl/克的聚對酞 酸乙二酯予以薄片化。使用該薄片來進行紡絲時之濾壓上 昇、以及拉伸時之斷絲之評量。評量結果係示於表5中。 (比較例5 -1〜5 - 2 ) 除了變更觸媒以外，以和實施例5-1同樣的做法來聚合 聚酯。在各實施例及比較例中，使用來做爲觸媒之化合物 係分別示於表5。在該化合物最終所得到的聚合物中之各 金屬原子及磷原子之含量，係按照表5所示之量來添加。 添加量係因應在聚合中所使用的反應器之特性、及聚合條 件而適當地選定。聚合結果與紡絲時之濾壓上昇、以及拉 -107- 1276646 五、發明說明（1〇6) 伸時之斷絲之評量結果係示於表5中。 [表5] 由上述之實施例和比較例可明白：當聚酯中金屬之含量 乃在本發明申請專利範圍內之物時，其紡絲和拉伸之作業 性係均優異；相對的，在本發明之申請專利範圍之外者， 當紡絲時會引起濾壓顯著地上昇、拉伸時也常發生斷絲， 作業性屬不良之結果。 (實施例6-1) (聚酯聚合例） 將高純度的對酞酸與其2倍量之乙二醇投入2升之附有 攪拌機的不銹鋼製高壓釜中，加入相對於酸成分計爲0.3 莫耳％之三乙胺，於0.25 Mpa.之加壓、245 °C下，一邊餾 去系統外部之水，一邊進行酯化反應120分鐘，而得到雙 (2 -羥乙基）對酞酸酯和寡聚物之混合物。對該混合物加入 2 · 5克/升之三乙醯乙酸鋁的乙二醇溶液、相對於酸成分計 爲0.07莫耳％之鋁原子，及10克/升之上述磷化合物A的 乙二醇溶液、相對於酸成分計爲0.2莫耳％之磷原子所做 成之聚縮合觸媒，於氮氛圍氣、常壓245°C下，攪拌10分 鐘。接著，花50分鐘昇溫至275°C爲止，慢慢地將反應系 壓力下降爲0.1托利，進一步在27 5°C、0.1托利進行聚 縮合反應。將聚對酞酸乙二酯到達0.65 dl/克所需要的聚 合時間示於表6中。 (實施例6 - 2 ~ 6 - 3、比較例6 -1〜6 - 3 ) -1 0 8 - 1276646 五、發明說明（1〇7 ) 除了變更觸媒以外，以和實施例6 -1同樣的做法來聚合 聚酯。在各實施例及比較例中，使用來做爲觸媒之化合物 係分別示於表6。添加量，係以相對於酸成分計之鋁原子 及磷原子之量來表示。聚合結果係示於表6中。磷化合物 A係使用以上所述之物，而Iragnox 1 425係使用汽巴· 特殊化學品公司製之物。在比較例6 - 3中，雖然進行聚合 達1 20分鐘以上，但仍達不到預定的黏滯度。 (實施例6-4) 將三乙醯乙酸鋁和Iragnox 1425預先混合在乙二醇中 ，調製成溶液以做爲聚縮合觸媒來使用。除了添加該溶液 做成之觸媒之外，利用和實施例6-3同樣的做法來聚合聚 酯。該聚對酞酸乙二酯之IV到達0.65 dl/克所需要的聚 合時間，係如實施例6 - 3同樣的結果。 [表6] 由上述之實施例和比較例可明白：當鋁化合物和磷化合 物之添加量乃在本發明申請專利範圍內之物時，觸媒活性 係爲優異，從而聚酯之生產性也優良；相對的，在本發明 之申請專利範圍之外者，觸媒活性不佳，聚酯之生產性也 變差。 (實施例7-1) (聚酯聚合例） 將高純度的對酞酸與其2倍量之乙二醇投入2升之附有 攪拌機的不銹鋼製高壓釜中，加入相對於酸成分計爲〇 . 3 -109- 1276646 五、發明說明（1〇8) 莫耳％之三乙胺，於0.25 Mpa之加壓、245°C下，一邊餾 去系統外部之水，一邊進行酯化反應1 2 0分鐘’而得到雙 (2 -羥乙基）對酞酸酯和寡聚物之混合物。對該混合物加入 2.5克/升之三乙醯乙酸鋁的乙二醇溶液、相對於酸成分計 爲0.014莫耳％之鋁原子，及1〇克/升之上述磷化合物A 的乙二醇溶液、相對於酸成分計爲〇·〇3莫耳％之磷原子， 以及50克/升之醋酸鋰二水合物的乙二醇溶液、相對於酸 成分計爲0.01莫耳％之鋰原子所做成之聚縮合觸媒’於氮 氛圍氣、常壓245°C下，攪拌10分鐘。接著，花50分鐘 昇溫至275°C爲止，慢慢地將反應系壓力下降爲〇·1托利 ，進一步在27 5 °C、0.1托利進行聚縮合反應。將聚對酞 酸乙二酯到達0.65 dl/克所需要的聚合時間（AP)示於表7 中〇 又，依照常法將在上述之聚縮合中所得到之IV爲 0.65 dl/克的聚對酞酸乙二酯予以薄片化。使用該PET樹 脂薄片來求得熱安定性參數（TS )和熱氧化安定性參數（TOS ) 。將結果係示於表7中。 又，使用上述PET樹脂薄片製膜成薄膜，做成回收之九 粒，並以回收九粒來進行薄膜之製膜。將薄膜之熱安定性 和熱老化性之評量結果示於表7中。 本發明之觸媒係具有高的觸媒活性，而且由使用它所得 到的PET製成之薄膜，其熱安定性和耐熱老化性兩者均爲 優良之物。 -110- 1276646 五、發明說明（1〇9) (實施例7-2) (磷化合物之合成例） 以下述式（化45)所代表之磷化合物（磷化合物B)之合成 [化4 5] Q : 〇f \—CH2-P—〇H•一 OC2H5 1. (1-萘基）甲基膦酸二乙基酯之合成 於氮氣氛圍氣下，以200°C (外溫）將8.31克（50毫莫 耳）亞磷酸三乙酯和8.83克（50毫莫耳）1-氯甲基萘之混合 物加熱，使發生氣體（EtCl )直到終了歷約30分鐘。冷卻 到室溫後，得到10.38克（粗收率75%)之（1-萘基）甲基膦 酸二乙基酯的無色油狀液體。 'H-NMR (CDCi3, 5)：1.151(6Hf t), 3.64K2H, d), 3.948(4H. m)t 7.381-7.579(4 H, m), 7.749-7.867(2H, m), 8. 088-8.133(1H, .m) 2. 鈉[0-乙基（1-萘基）甲基膦酸酯]之合成 在6.5克（84毫莫耳）50%氫氧化鈉和6.1毫升甲醇之混 合溶液中，加入6.1毫升之含5克（18毫莫耳）之（1-萘基） 甲基膦酸二乙基酯之甲醇溶液，於氮氣氛圍氣下，進行迴 流加熱2 4小時。反應後’一邊冷卻反應混合物，一邊加 入6.59克（63毫莫耳）之濃鹽酸，取出析出以異丙醇予以 洗淨後，減壓餾除過濾液。將所得到的殘渣溶解在熱異丙 -111 - 1276646 五、發明說明（110) 醇中，取出不溶分，減壓餾除異丙醇後，以熱η -庚烷洗淨 殘渣，乾燥之而得到3 · 8克（78%)之鈉[0-乙基（1-萘基）甲 基膦酸酯]。 形狀：針狀結晶； 熔點：277〜281°C (分解） ^NMR (DMS0-d6, 5) :0.961 (3H, t, J-7Hz), 3.223(2H, d), 3.589(2Hr m), 7.3 65-7.468(4H, m. J=7Hz), 7. 651-8.314(3H( m) „ 3. 0-乙基（1-萘基）甲基膦酸（磷化合物B)之合成 在室溫攪拌下，於10毫升之含1克（3.7毫莫耳）之鈉 [0-乙基（1-萘基）甲基膦酸酯]的水溶液中，加入1.9克濃 鹽酸，攪拌1小時。以萃取出反應混合物、水洗甲苯相後 、減壓餾甲苯，而得到497毫克（54%)之0-乙基（1-萘基） 甲基膦酸。 形狀：無色油狀液體； ΐ-ΝΜβ (CDC13? δ)：1.085(3Η. t, J-7Hz)； 3.450(2Ht d), 3.719(2H, m, 7Hz), 7. 369-7.532(4H. m), 7.727-8.043(3H, m), 10..939(1H, s) (聚酯聚合例） 除了變更觸媒以外，以和實施例7 - 1同樣的做法來聚合 聚酯。使用來做爲觸媒之化合物、與添加量係示於表7中 。鋁化合物之添加量，係以柑對於酸成分計之鋁原子的添 加量來表示；而磷化合物B之添加量，係以相對於酸成分 計之磷原子的添加量來表示。將聚對酞酸乙二酯之IV到 達0.65 dl/克所需要的聚合時間（AP)示於表7中。 -112- 1276646 五、發明說明（111 ) 又，依照常法將在上述之聚縮合中所得到之IV爲 0.65 dl/克的聚對酞酸乙二酯予以薄片化。使用該PET樹 脂薄片來求得熱安定性參數（TS)和熱氧化安定性參數（TOS) 。將結果係示於表7中。 又，使用上述PET樹脂薄片製膜成薄膜，做成回收之九 粒，並以回收九粒來進行薄膜之製膜。將薄膜之熱安定性 和熱老化性之評量結果示於表7中。 本發明之觸媒係具有高的觸媒活性，而且由使用它所得 到的PET製成之薄膜，其熱安定性和耐熱老化性兩者均爲 優良之物。 (比較例7 -1 ) 除了使用三氧化銻（其添加量以相對於PET中酸成分計 之銻原子係爲0.05莫耳％)來做爲觸媒以外，均以和實施 例7-1同樣的操作方式來進行。三氧化銻係使用市售之銻 (瓜）氧化物（阿爾得利汽化學品公司製，純度爲99.999%) 。所使用的三氧化銻，係攪拌約1小時使之溶解在150°C 之乙二醇中而成爲濃度約爲1〇克/升之溶液。將聚對酞酸 乙二酯之IV到達0.65 dl/克所需要的聚合時間（AP)示於 表7中。 又，依照常法將在上述之聚縮合中所得到之IV爲0.65 d 1 /克的聚對酞酸乙二酯予以薄片化。使用該PET樹脂薄 片來求得熱安定性參數（TS )和熱氧化安定性參數（TOS )。 將結果係示於表7中。 -113- 1276646 五、發明說明（112) 又，使用上述PET樹脂薄片製膜成薄膜，做成回收之九 粒，並以回收九粒來進行薄膜之製膜。將薄膜之熱安定性 和熱老化性之評量結果示於表7中。 雖然本發明之觸媒係具有優良的觸媒活性，但是由使用 它所得到的PET製成之薄膜，其熱安定性卻比實施例中之 物要來得差。 (比較例7_2) 除了在比較例7 - 1之觸媒中，進一步添加磷化合物A(其 添加量以相對於PET中酸成分計之磷原子係爲0 · 03莫耳％) 以外，均以和實施例7 -1同樣的操作方式來進行。三氧化 銻係使用市售之銻（瓜）氧化物（阿爾得利汽化學品公司製 ，純度爲99.9 9 9%)。所使用的三氧化銻，係攪拌使之溶解 在150°C之乙二醇中而成爲濃度約爲10克/升之溶液。將 聚對酞酸乙二酯之IV到達0.65 dl/克所需要的聚合時間 (AP)示於表7中。該三氧化銻之觸媒活性之變化，並無法 因與磷化合物A倂用而被確認出來。 (比較例7-3) 除了使用二氧化銷（其添加量以相對於PET中酸成分計 之鉻原子係爲0.03莫耳％)來做爲觸媒以外，以和實施例 7 -1同樣的操作方式來進行。將聚對酞酸乙二酯之IV到達 0.65 dl /克所需要的聚合時間（AP)示於表7中。 又，依照常法將在上述之聚縮合中所得到之IV爲0.65 d 1 /克的聚對酞酸乙二酯予以薄片化。使用該PET樹脂薄 -114- 1276646 五、發明說明（113) 片來求得熱安定性參數（TS )和熱氧化安定性參數（TOS )。 將結果係示於表7中。 又，使用上述PET樹脂薄片製膜成薄膜，做成回收之九 粒，並以回收九粒來進行薄膜之製膜。將薄膜之熱安定性 和熱老化性之評量結果示於表7中。 雖然本發明之觸媒係具有優良的觸媒活性，但是由使用 它所得到的PET製成之薄膜，其熱安定性及耐熱老化性卻 比實施例中之物要來得差。 (比較例7-4) .除了使用乙酸乙醯鋁（其添加量以相對於PET中酸成分 計之鋁原子係爲0.014莫耳％)來做爲觸媒以外，均以和實 施例7-1同樣的操作方式來進行。雖然加熱進行聚合歷 150分鐘以上，聚對酞酸乙二酯之IV仍無法達到0.65 d 1 / 克。 (比較例7-5) 除了使用乙酸鋰二水合物（其添加量以相對於PET中酸 成分計之鋰原子係爲0.01莫耳％)來做爲觸媒以外，均以 和實施例7-1同樣的操作方式來進行。雖然加熱進行聚合 歷150分鐘以上，聚對酞酸乙二酯之IV仍無法達到0.6 5 dl /克。 [表7] 由上述之實施例和比較例可明白··當PET樹脂薄片之熱 安定性參數乃在本發明申請專利範圍內之物時’則薄膜之 -115- 1276646 五、發明說明（114) 熱安定性會變得優，而薄膜之品質也會變得優良；且碎屑 薄膜之再利用品質亦爲優良。一方面，在本發明申請專利 範圍外者，則薄膜之熱安定性會變差，且碎屑薄膜之再利 用品質亦爲不良。 又，雖然原本鋁化合物及鋰化合物之觸媒活性均不佳， 但是使之與磷化合物共存的本發明觸媒之活性卻是優良的 ，所得到的聚酯亦爲熱安定性優良之物。一方面，使磷化 合物與銻化合物共存利用時，銻化合物之觸媒活性卻不受 影響ώ (實施例8-1) (鹽基性醋酸鋁之水溶液的調製例） 將1克之鹽基性醋酸鋁（羥基鋁二乙酸鹽；阿爾得利汽 製）對50毫升之比例加入去離子水，於常溫下攪約12小 時。之後，一邊慢慢地提高液溫，一邊續繼攪拌。當液溫 到達約60°C時，保持在該溫度點攪拌約2小時，進一步地 提高液溫並續繼攪拌。當液溫到達約75t時，保持在該溫 度點攪拌約2小時以上，而得到透明的水溶液。 (聚酯聚合例） 對依照常法從高純度的對酞酸與其2倍莫耳量之乙二醇 製造得到之雙（2-羥乙基）對酞酸酯和寡聚物之混合物，加 入相對於聚酯之中之酸成分計鋁原子爲0.035莫耳％之上 述鹽基性醋酸鋁水溶液，及10克/升之Irganox 1 425 (汽 巴•特殊化學品公司製）的相對於酸成分計爲0.02莫耳％ -1 1 6 - 1276646 五、發明說明（115) 之乙二醇溶液所做成之聚縮合觸媒，於氮氛圍氣、常壓、 245°C下，攪拌15分鐘。接著，花55分鐘昇溫至27 5°C爲 止，慢慢地將反應系壓力下降爲66.5巴（0.5托利），進 一步在2751、66.5巴進行聚縮合反應90分鐘。將所得 到的PET之IV和Tm示於表8中。 (實施例8-2) (鹽基性醋酸鋁之乙二醇溶液的調製例） 將鹽基性醋酸鋁（CH3COOAl(OH)2 · 1/3H3B03 ;阿爾得利 汽製）於乙二醇中攪拌約12小時以上，而得到濃度約爲5 克/升的乙二醇溶液。 (聚酯聚合例） 除了以相對於聚酯之中之酸成分計鋁原子爲0.035莫耳 %之上述鹽基性醋酸鋁之乙二醇溶液，及1 〇克/升之 Irganox 1 425 (汽巴•特殊化學品公司製）的相對於酸成 分計爲0.02莫耳％之乙二醇溶液來做爲聚縮合觸媒以外， 均以和實施例8 - 1同樣的做法來進行操作。將所得到的 PET之IV和Tm示於表8中。 (比較例8 -1 ) 除了以相對於聚酯之中之酸成分計鋁原子爲0.03 5莫耳 %之鹽基性醋酸鋁（羥基鋁二乙酸鹽）之約10克/升的乙二 醇溶液，及10克/升之Irganox 1425 (汽巴•特殊化學品 公司製）的相對於酸成分計爲0 · 0 2莫耳％之乙二醇溶液來 做爲聚縮合觸媒以外，均以和實施例8 -1同樣的做法來進 -117- 1276646 五、發明說明（116) 行操作。將所得到的PET之iy和Tm示於表8中。 (實施例8 - 3 ) (鹽基性醋酸鋁之乙二醇溶液的調製例） 將1克的以約1/16莫耳量之硼酸予以安定化之鹽基性 醋酸鋁對50毫升之比例加入去離子水，於常溫下攪約12 小時。之後，以約70°C攪拌約2小時，而得到透明的水溶 液。將容量比爲2倍量之乙二醇加入到該水溶液中，於室 溫攪拌數小時。之後，一邊於1 00°C將該溶液攪拌數小時 ，一邊從系統餾除水分而得到乙二醇溶液。 (聚酯聚合例） 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2 -羥乙基）對酞酸酯和寡聚物之混合物，加入相對於聚酯 之中之酸成分計鋁原子爲0.014莫耳％之上述鹽基性醋酸 鋁的乙二醇溶液，及10克/升之Irganox 1425 (汽巴•特 殊化學品公司製）的相對於酸成分計爲0.02莫耳％之乙二 醇溶液所做成之聚縮合觸媒，於氮氛圍氣、常壓、245 °C 下，攪拌10分鐘。接著，花45分鐘昇溫至275°C爲止， 慢慢地將反應系壓力下降爲66 · 5巴（0 · 5托利），進一步 在275°C、66.5巴進行聚縮合反應20分鐘，而得到IV 爲 0 . 38 dl /克的 PET。 (實施例8-4) (鹽基性醋酸鋁之水/乙二醇混合溶液的調製例） 將1克之鹽基性醋酸鋁（經基鋁二乙酸鹽；阿爾得利汽 -118- 1276646 五、發明說明（117) 製）對5 0晕:升之比例加入去離子水，於常溫下攪約1 2小 時。之後，以約70°C攪拌約6小時，而得到透明的水溶液 。以相對於該水溶液爲3倍量（容量比）將乙二醇添加到該 水溶液中’於室溫下攪拌6小時而得到觸媒溶液。 (聚酯聚合例） 將高純度的對酞酸與其2倍量之乙二醇投入2升之附有 攪拌機之熱循環式的不銹鋼製高壓釜中，加入相對於酸成 分計爲0.3莫耳％之三乙胺，於0.25 Mpa之加壓、250°C 下’一邊飽去系統外部之水，一邊進行酯化反應11 5分鐘 ，而得到酯化爲95%以上之雙（2-羥乙基）對酞酸酯（BHET) 和寡聚物之混合物（以下，稱爲BHET混合物）。對該BHET 混合物加入相對於聚酯之中之酸成分計鋁原子爲0.014莫 耳％之上述鹽基性醋酸鋁的水/乙二醇混合溶液，及100克 /升之Irganox 1425 (汽巴•特殊化學品公司製）的相對於 酸成分計爲0.01莫耳％之乙二醇溶液所做成之聚縮合觸媒 ，於氮氛圍氣、常壓、25CTC下，攪拌15分鐘。接著，花 60分鐘昇溫至275 t爲止，慢慢地將反應系壓力下降爲 66.5巴（〇·5托利），進一步在27 5°C、66.5巴進行聚 縮合反應132分鐘，而得到IV爲0.61 dl/克的PET，本 發明係爲具有實用的觸媒活性之物質。將所得到的PET物 性示於表9中。 (實施例8 - 5 ) (鹽基性醋酸鋁之乙二醇溶液的調製例） -119- 1276646 五、發明說明（118) 將上述鹽基性醋酸鋁之水/乙二醇溶液，一邊於90〜 1 l〇°C下攪約數小時，一邊從系統餾除水分。結果，得到 濃度約爲6 · 5克/升之乙二醇溶液。 (聚酯聚合例） 除了加入相對於聚酯中之酸成分計鋁原子爲0.〇14莫耳 %之上述鹽基性醋酸鋁的乙二醇溶液，及丨00克/升之 Irganox 1425 (汽巴•特殊化學品公司製）的相對於酸成 分計爲0.01莫耳％之乙二醇溶液所做成之聚縮合觸媒以外 ，均以和實施例8 - 4同樣的做法來聚合聚酯。聚合時間爲 133分鐘，而得到IV爲0.60 dl/克的PET。將所得到的 PET物性示於表9中。 (實施例8 - 6 ) (鹽基性醋酸鋁之乙二醇溶液的調製例） 將鹽基性醋酸鋁（ch3cooai(oh)2 · i/3h3bo3 ;阿爾得利 汽製）於乙二醇中，以約70°C攪拌5小時，而得到濃度約 爲5克/升的乙二醇溶液。 (聚酯聚合例） 對依照常法從高純度的對酞酸與乙二醇製造得到之雙 (2 -羥乙基）對酞酸酯和寡聚物之混合物，加入相對於聚酯 之中之酸成分計鋁原子爲0.014莫耳％之上述鹽基性醋酸 鋁的5克/升之乙二醇溶液，及1〇克/升之I rganox 1425 (汽巴•特殊化學品公司製）的相對於酸成分計爲〇 . 〇 1莫 耳％之乙二醇溶液所做成之聚縮合觸媒，於氮氛圍氣、常 -120- 1276646 五、發明說明（1 19 ) 壓' 24 5 °C下，攪拌1〇分鐘。接著，花50分鐘昇溫至 275°C爲止，慢慢地將反應系壓力下降爲13.3巴（0·ι托 利）’進一步在27 5°C、13.3巴進行聚縮合反應90分鐘 ’而得到IV爲0 · 6 5 d 1 /克的PET。所得到的PET之AV爲 2當量/噸，Tm爲25 6°C，L値爲68.9，a値爲- 2.3，b値 爲 4 · 2 〇 (實施例8 - 7 ) (乳酸鋁之乙二醇溶液的調製例） 將乳酸鋁調製成約67克/升之水溶液。之後，加入乙二 醇’於約10(TC加熱以餾除水分，而得到約爲29克/升的 乙二醇溶液。 (聚酯聚合例） 除了加入相對於聚酯中之酸成分計鋁原子爲0 · 0 1 4莫耳 %之上述乳酸鋁的乙二醇溶液，及1〇〇克/升之Irganox 1 425 (汽巴•特殊化學品公司製）的相對於酸成分計爲 0.01莫耳％之乙二醇溶液所做成之聚縮合觸媒以外，均以 和實施例8 - 4同樣的做法來聚合聚酯。聚合時間爲1 24分 鐘，而得到IV爲〇 · 6 d 1 /克的PET。將所得到的PET物性 示於表9中。 (比較例8 - 2 ) 除了加入相對於聚酯中之酸成分計鋁原子爲0 . 0 1 4莫耳 %之約5克/升之乳酸鋁的乙二醇溶液，及100克/升之 Irganox 1425 (汽巴•特殊化學品公司製）的相對於酸成 分計爲0·01莫耳％之乙二醇溶液所做成之聚縮合觸媒以外 -121- 1276646 五、發明說明（120) ’均以和實施例8 - 4同樣的做法來聚合聚酯。聚合時間爲 168分鐘’而得到IV爲0.61 dl /克的pet，觸媒活性不良 之物。 (評量結果） 由上述之實施例和比較例可明白：當使用溶解殘酸銘之 溶液來做爲觸媒之情況下，任一種情形其聚合活性均爲優 良，所得到的聚酯亦爲品質優良之物；相對的，當使用不 溶解羧酸鋁之溶液來做爲觸媒之情況下，將會得到聚合活 性不佳之結果。 [表8] [表9] 【產業上利用之領域】 本發明聚酯之可能應用範圍，例如是以衣料用纖維、窗 簾、地毯、寢具等所代表之內部·寢裝用纖維；以輪胎帘 子線、繩等所代表之產業資材用纖維；各種織物、各種編 物、短纖維不織布、長纖維不織布等之纖維、包裝用薄膜 、工業用用薄膜、光學用薄膜、磁帶用薄膜、照相用薄膜 、罐積層用薄膜、冷凝用薄膜、熱收縮用薄膜、氣障薄膜 、白色薄膜、易切割薄膜、非耐熱拉伸瓶、耐熱拉伸瓶、 直接吹瓶、氣障瓶、耐壓瓶、耐熱壓瓶等之中空成形體、 A-PET或C-PET等之席片、玻璃纖維強化聚酯、單性體等 所代表之工程塑膠等之各種成形物、以及塗料或黏著劑等 -122- 1276646 五、發明說明（121) 1) 破一^抖激蹯丑睁_缅屮N.i。 2) 樹13抖類1§丑鄹睁酗缅屮芑黥屮咏|1钿屮^霧·,。 比較例1 -1 實施例1-3 實施例卜2 實施例1-1 醋酸鈉 三乙酸乙醯鋁 磷酸 S [11 Μ 冷（Ν驟 卟隳蹯 ^ [Ν |[ > _兴 醋酸鈉 氯化鋁 Irganox 1425 s iii m 冷（N隳 豸（N >爾 化合物 1 1 0〇 U\ to Η-* CM ο *<1 鹼金屬含量 (莫耳)υ 1 1 ο ^ty 1 驗土金屬含量 (莫耳)υ 0〇 to to ο ο *<1 Μ (莫耳)2) g K) κ> to 鋁含量 (pprn) On to 〇\ υο LO 磷含量： (ppm) Os ON ON LO 0〇 聚合時間/分 X > 〇 〇 濾壓上昇 X D> 〇 〇 斷絲 【姗一〕-97- 1276646 V. INSTRUCTIONS (96) Synthesis of sodium (0-ethyl 3,5-di-t-butyl-4-hydroxyphenylphosphonate) at 6. 5 grams (84 millimoles) of 50% sodium hydroxide and 6. 5 g (14 mmol) of diethyl (3,5-di-tri-butyl-4-hydroxy)phosphonate (Iragnoxl 222, Ciba Specialty Chemicals) was added to a mixed solution of 1 ml of methanol. The methanol solution of the company was heated under reflux for 24 hours under a nitrogen atmosphere. After the reaction, while cooling the reaction mixture, it was added 7. 33 g (70 mmol) of concentrated hydrochloric acid was taken out and precipitated, washed with isopropyl alcohol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, and the insoluble fraction was taken out, and the isopropyl alcohol was distilled off under reduced pressure, and then the residue was washed with hot heptane and dried to give 3. 4 g (69%) of sodium (0-ethyl 3,5-di-t-butyl-4-hydroxyphosphonate). Shape: white powder; melting point: 294~302 ° C (decomposition) lH-NMR (d6-DMSO, δ): 1. 078 (3H, t, J = 7Hz), 1. 354 (18H, s), 2. 71K2H, d), 3 · 724 (2Η. m· J=7Hz),6·626(1Η, s),, 6. 9665(2H, s) Elemental analysis (theoretical 括 in brackets): Na: 6.66% (6·56%), P: 9. 18% (8. 84%) Synthesis of 0-ethyl 3,5-di-t-butyl-4-hydroxyphosphonic acid (phosphonium phosphide) 1 gram in 20 ml with stirring at room temperature (2. Add 8 ml of sodium (0-ethyl 3,5-di-tetra-butyl-4-hydroxyphenylphosphonate) to an aqueous solution. 5 g of concentrated hydrochloric acid was stirred for 1 hour. 150 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, washed with water and dried to give <RTI ID=0.0>> - hydroxyphosphonic acid. -98- 1276646 V. INSTRUCTIONS (97) Shape: plate crystal; melting point: 126~127°C • · · - * β-NMR (CDC13, 5): 1·207 (3Η, t, J=7Hz) , 1.436 (18Η, s), ················ 88 8 (2H, m, J=7Hz), 7. 088(2H, s), 7. 679-8,275 (lH, br). (Polyester polymerization example) Using a 2 liter stainless steel autoclave with a stirrer, bis(2-hydroxyethyl)terephthalate and a bis(2-hydroxyethyl)terephthalate obtained by high-purity citric acid and ethylene glycol according to a conventional method were used. a mixture of oligomers, added 2 . 5 g / liter of ethylene glycol solution of aluminum triacetate, and 20 g / liter of the above ethylene compound solution of phosphorus compound A, and 50 g / liter of sodium acetate in ethylene glycol solution Condensation catalyst. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 1. The amount of the metal component added to the catalyst is at least the same as that obtained according to the analysis result of the vaporization during the polymerization, but the added phosphorus component is more than the analysis during the polymerization and the volatilization during the formation. result. Further, the amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 245 °C. Next, the temperature was raised to 275 ° C in 50 minutes, and the reaction system pressure was gradually lowered to 0. 1 Toli, further at 275 ° C, 0. 1 Toli A polycondensation reaction is carried out. The polyethylene terephthalate reaches 0. The required polymerization time of 65 dl/g is shown in Table 1. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was thinned. That is, at the point when the melt polymerization reaches a predetermined stirring torque, nitrogen gas is introduced into the autoclave, returned to normal pressure, and after the polycondensation reaction is stopped, -99-1276646, and the invention (98) is about 0. Under the pressure of 1 Mpa, the molten polymer was continuously extruded into a bundle shape in the lower part of the reaction tank, quenched in cold water, and cut into a cylindrical sheet of about 3 mm and a diameter of about 2 mm by a cutter. . The hold time in cold water is about 20 seconds. This sheet was used to measure the physical properties of pet. As a result, IV was 〇·65 dl/g, acid bismuth was 2 equivalent/ton, and DEG was 2. 1 Mole %, Tm is 256. At 6 ° C, the Tel is 166. 0 ° C, Tc2 is 188. 6 ° C. Also, L 値 is 66. 0, a 値 is -1·8, and b 値 is 3. 6. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 1. (Examples 1-2 to 1-3, Comparative Example 1-1) A polyester was polymerized in the same manner as in Example 1-1 except that the catalyst was changed. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 1. The content of each of the metal atoms and phosphorus atoms in the polymer finally obtained from the compound was added in an amount shown in Table 1. The results of the polymerization of the examples and the comparative examples, the increase in the filtration pressure at the time of spinning, and the evaluation results of the broken yarn at the time of stretching are shown in Table 1. Iragnox 1425 was produced by Ciba Specialty Chemicals Co., Ltd., and phosphorus compound A was synthesized in the same manner as in Example 1-1. [Table 1] It can be understood from the above examples and comparative examples that when the content of the metal in the polyester is within the scope of the patent application of the present invention, both the spinning and the stretching workability are excellent; In addition to the scope of the patent application of the present invention, as a result, the filtration pressure is remarkably increased when spinning, and the elongation is often caused when stretching -100-1276646. . (Example 2-1) A mixture of bis(2-hydroxyethyl)-p- phthalate and an oligomer produced by high-purity citric acid and ethylene glycol according to a conventional method was added. A polycondensation catalyst made of 5 g/liter of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 50 g/liter of lithium acetate dihydrate. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 2. However, the content is expressed as a metal atom relative to the acid component in the polymer, expressed in mol%. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, the mixture was stirred under a nitrogen atmosphere at normal pressure at 245 ° C for 10 minutes. Then, after heating for 50 minutes to 275 ° C, the pressure of the reaction system was slowly lowered to 0. 1 Toli, further at 27 5 °C, 0. 1 Tory undergoes a polycondensation reaction. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 2. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 2. (Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-2) The polyester was polymerized in the same manner as in Example 2-1 except that the catalyst was changed. . The results are shown in Table 2. In Examples 2 - 6, magnesium acetate and aluminum acetate were added as a polycondensation catalyst, and 0,01 mol% of dimethyl phenylsulfonate was added with respect to the acid component in the polymer. -101- 1276646 V. INSTRUCTION OF THE INVENTION (1) [Table 2] It is understood from the above examples and comparative examples that when the content of the metal in the polyester is within the scope of the patent application of the present invention, the spinning thereof And the workability of the stretching is excellent; in contrast, outside the scope of the patent application of the present invention, the spinning pressure is remarkably increased when spinning, and the yarn breakage often occurs during stretching, and the workability is poor. . (Example 3-1) A mixture of bis(2-hydroxyethyl)-p- phthalate and an oligomer produced by high-purity citric acid and ethylene glycol according to a conventional method was added. A polycondensation catalyst made of 5 g/L of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 10 g/L of Iragnox 1 425 (manufactured by Ciba Specialty Chemicals Co., Ltd.). The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 3. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 245 °C. Then, after heating for 50 minutes to 275 ° C, slowly reduce the pressure of the reaction system to 0. 1 Toli, further at 275 °C, 〇. 1 Tory undergoes a polycondensation reaction. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 3. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. The sheet was used to determine the physical properties of PET. As a result, IV is 0. 65 dl / gram, acid equivalent is 6 equivalent / ton, DEG is 2. 1% by mole, Tm is 256. 3 ° C, Tc2 is 186. 2 ° C. Also, L 値 is 68_9, -102-1276646. V. Description of invention (1〇1) a 値 is -2. 56,b 値 is 5. 49. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 3. (Examples 3 - 2 to 3 - 9, Comparative Examples 3 - 1 to 3 - 3) Polyester was polymerized in the same manner as in Example 3-1 except that the catalyst was changed. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 3, respectively. The content of each of the metal atoms and phosphorus atoms in the polymer finally obtained from the compound was added in an amount shown in Table 3. The amount of addition is appropriately selected in accordance with the characteristics of the reactor used in the polymerization and the polymerization conditions. In Examples 3 - 9, ruthenium trioxide was used as a catalyst. Antimony trioxide is added in accordance with the amount of germanium atoms in the finally obtained polymer. The results of the polymerization of each of the examples and the comparative examples, the increase in the filtration pressure at the time of spinning, and the evaluation results of the broken yarn at the time of stretching are shown in Table 3. Iragnox 1425 is made from Ciba Specialty Chemicals, and Phosphorus A is synthesized using the methods described above. [Table 3] It can be understood from the above examples and comparative examples that when the content of the metal in the polyester is within the scope of the present invention, both the spinning and the stretching workability are excellent; In addition to the scope of the patent application of the present invention, as a result, the filtration pressure is remarkably increased during spinning, and the yarn breakage often occurs during stretching, and the workability is poor. (Example 4-1) A bis-103-1276646 which is produced from a high-purity citric acid and ethylene glycol according to a conventional method. 5. Description of the invention (1〇2) (2-hydroxyethyl)-p- phthalate And a mixture of oligomers, adding 13 g / liter of aluminum trichloride in ethylene glycol solution, relative to the acid composition of the polyester, the aluminum atom is 0. 143 mol%, and 10 g/l of Iragnox 1425 (made by Ciba Specialty Chemicals Co., Ltd.), the ethylene glycol solution relative to the acid content of the polyester Iragnox 1425 is 0. The polycondensation catalyst made of 022 mol% was stirred for 10 minutes under nitrogen atmosphere at normal pressure at 245 °C. Then, after heating for 50 minutes to 27 5 °C, slowly reduce the pressure of the reaction system to 0. 1 Tory, further at 27 5 °C, 0. 1 Tory undergoes a polycondensation reaction. The poly(p-ethylene phthalate) reaches 0. The polymerization time required for 65 dl/g is shown in Table 4. The PET resin sheet contained 45 ppm of calcium atoms, and the total content of metal atoms was 65 ppm. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 4. (Example 4-2) (Synthesis Example of Phosphorus Compound) Synthesis of a phosphorus compound (NMPA) represented by the following formula (2 1 ) Under a nitrogen gas atmosphere, 8. 31 grams (50 millimoles) of triethyl phosphite, and 8. A mixture of 83 g (50 mmol) of 1-methyl chloroformate produced a gas (C2H5C1) which was finally heated at 200 ° C (external temperature) for about 30 minutes. After cooling to room temperature, it was obtained. 38 g (75% crude yield) of a colorless oily liquid. ^-NMR (CDCls; 5): 1. 151 (6H, t), 3. 64K2H; d), ' 3. 948 (4H. m), 7. 381-7. 579(4 H, m). 7. 749-7. 867(2H, m), 8. 088-8. 133(1H, m). (Polymer polymerization example) Polymerization was carried out in the same manner as in Example 4-1 except that the catalyst was changed. -104-!276646 5. Inventive Note (103) Polyester. In this embodiment, an ethylene glycol solution of 2.5 g/L of aluminum triacetate is used, and the aluminum atom is 〇·〇1 4 mol% relative to the acid component of the polyester, relative to the polyester. The acid component is counted as 0. 014 mol% of 50 g / l of the above NMPA glycol solution, and 0. 02% of the moles converted into polyester is 0. 1% by weight of Iragnox 1 330 (made by Ciba Specialty Chemicals Co., Ltd.), an ethylene glycol solution of 50 g/L of lithium acetate dihydrate, and a lithium atom based on the acid component of the polyester. Hey. 〇 1 mol% of the compound is used as a polycondensation catalyst. The polyethylene terephthalate reaches 0. The polymerization time required at 65 dl/g, the result of measuring the amount of aluminum atoms and the amount of phosphorus atoms contained in the obtained PET resin sheet, and the aluminum atomic ratio with respect to the phosphorus atom are shown in Table 4. The amount of lithium atoms contained in the PET resin sheet was 4 ppm, so that the total content of metal atoms was 24 ppm. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 4. (Comparative Example 4 -1) A polyester was polymerized in the same manner as in Example 4-1 except that the catalyst was changed. Using an ethylene glycol solution of 13 g/L of aluminum chloride, the aluminum atom is 0 with respect to the acid component of the polyester. 015 mol%, 50 g / liter of lithium acetate dihydrate in ethylene glycol solution, relative to the acid component of the polyester, the lithium atom is 0. 06 Moer% of the compound is used as a polycondensation catalyst. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 4. The use of such a PET resin sheet for the filtration at the time of spinning -105-1276646 V. Description of the invention (1〇4) Evaluation of the rise and breakage of the yarn. The results of the evaluation are shown in Table 4. [Table 4] From the above examples and comparative examples, it is understood that a polyester polymerized with an aluminum compound, a phosphorus compound, and a phenol compound is used when the content of the metal in the polyester is within the scope of the present patent application. It has excellent workability in spinning and stretching. On the other hand, in the case where a phosphorus compound or a phenol-based compound is not used, the thermal oxidation stability is deteriorated, and at the same time, the filtration pressure is remarkably increased during spinning, and the yarn breakage often occurs during stretching, resulting in poor workability. (Example 5-1) To a mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer produced by high-purity p-citric acid and ethylene glycol according to a conventional method, was added. A polycondensation catalyst made of 5 g/liter of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 10 g/liter of the above phosphorus compound A. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 245 Torr. Then, after heating for 50 minutes to 275 ° C, slowly reduce the pressure of the reaction system to 0. 1 Toli, further at 27 5 ° C, 0. 1 Tory undergoes a polycondensation reaction. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 1. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. The sheet was used to determine the physical properties of PET. The results of the evaluation are shown in Table 5. -106- 1276646 V. INSTRUCTION DESCRIPTION (105) (Example 5-2) Bis(2-hydroxyethyl)-p-ruthenium ruthenate and oligosaccharide obtained from high-purity citric acid and ethylene glycol according to a conventional method a mixture of polymers, added 2. A polycondensation catalyst made of 5 g/L of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 10 g/L of Iragnox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.). The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 245 °C. Then, after heating for 50 minutes to 275 ° C, slowly reduce the pressure of the reaction system to 0. 1 Toli, further subjected to a polycondensation reaction at 275 ° C, 〇 1 Tory. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 1. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. This sheet was used to carry out the evaluation of the filtration pressure during spinning and the breaking of the yarn during stretching. The results of the evaluation are shown in Table 5. (Comparative Example 5 -1 to 5 - 2 ) A polyester was polymerized in the same manner as in Example 5-1 except that the catalyst was changed. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 5, respectively. The content of each of the metal atoms and phosphorus atoms in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected in accordance with the characteristics of the reactor used in the polymerization and the polymerization conditions. The results of the polymerization and the increase in the filtration pressure at the time of spinning, and the pull-107- 1276646 V. The description of the invention (1〇6) The results of the evaluation of the broken yarn at the time of stretching are shown in Table 5. [Table 5] From the above examples and comparative examples, it is understood that when the content of the metal in the polyester is within the scope of the present invention, both the spinning and the stretching work are excellent; In addition to the scope of the patent application of the present invention, the filtration pressure is remarkably increased during spinning, and the yarn breakage often occurs during stretching, and workability is a poor result. (Example 6-1) (Polyester polymerization example) High-purity citric acid and 2 times the amount of ethylene glycol were placed in a 2 liter stainless steel autoclave equipped with a stirrer, and the addition was 0 with respect to the acid component. . 3 mol% of triethylamine, at 0. 25 Mpa. The mixture was subjected to an esterification reaction for 120 minutes at 245 ° C while distilling off water outside the system to obtain a mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer. To the mixture was added 2 · 5 g / liter of ethylene glycol triacetate in ethylene glycol solution, relative to the acid composition of 0. 07 mol% of the aluminum atom, and 10 g / liter of the above phosphorus compound A of the ethylene glycol solution, relative to the acid component is 0. A polycondensation catalyst prepared by a phosphorus atom of 2 mol% was stirred in a nitrogen atmosphere at a normal pressure of 245 ° C for 10 minutes. Next, the temperature was raised to 275 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 0. 1 Toli, further at 27 5 ° C, 0. 1 Tory undergoes a polycondensation reaction. The polyethylene terephthalate reaches 0. The polymerization time required for 65 dl/g is shown in Table 6. (Example 6 - 2 to 6 - 3, Comparative Example 6 -1 to 6 - 3 ) -1 0 8 - 1276646 V. Description of the Invention (1〇7) The same as Example 6-1 except that the catalyst was changed. The practice to polymerize polyester. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 6, respectively. The amount of addition is expressed by the amount of aluminum atom and phosphorus atom based on the acid component. The polymerization results are shown in Table 6. Phosphorus compound A uses the above-mentioned materials, and Iragnox 1 425 uses a product manufactured by Ciba Specialty Chemicals. In Comparative Example 6-3, although the polymerization was carried out for more than 1 20 minutes, the predetermined viscosity was not obtained. (Example 6-4) Aluminum triacetate acetate and Iragnox 1425 were previously mixed in ethylene glycol to prepare a solution to be used as a polycondensation catalyst. The polyester was polymerized in the same manner as in Example 6-3 except that the catalyst was added with the solution. The IV of the polyethylene terephthalate reaches 0. The polymerization time required at 65 dl/g was the same as in Example 6-1. [Table 6] From the above examples and comparative examples, it is understood that when the amount of the aluminum compound and the phosphorus compound added is within the scope of the present invention, the catalyst activity is excellent, and the productivity of the polyester is also Excellent; in contrast, outside the scope of the patent application of the present invention, the catalytic activity is poor and the productivity of the polyester is also deteriorated. (Example 7-1) (Polyester polymerization example) High-purity citric acid and 2 times the amount of ethylene glycol were placed in a 2 liter stainless steel autoclave equipped with a stirrer, and the addition was based on the acid component. . 3 -109- 1276646 V. Description of the invention (1〇8) Mole% of triethylamine, at 0. A mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer was obtained by subjecting the water outside the system to water at 25 °C at 245 ° C for 1 to 20 minutes. Add to the mixture 2. 5 g / liter of ethylene glycol solution of aluminum triacetate, relative to the acid component is 0. 014 mole % of aluminum atom, and 1 gram per liter of the above-mentioned phosphorus compound A ethylene glycol solution, relative to the acid component, 〇·〇3 mol% of phosphorus atom, and 50 g/liter of lithium acetate The ethylene glycol solution of the dihydrate is 0. A polycondensation catalyst made of a lithium atom of 0.1 mol% was stirred in a nitrogen atmosphere at a normal pressure of 245 ° C for 10 minutes. Then, after heating for 50 minutes to 275 ° C, the pressure of the reaction system was gradually reduced to 〇·1 Toli, further at 27 5 ° C, 0. 1 Tory undergoes a polycondensation reaction. The polyethylene terephthalate reaches 0. The polymerization time (AP) required for 65 dl/g is shown in Table 7. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. The PET resin flakes were used to determine thermal stability parameters (TS) and thermal oxidation stability parameters (TOS). The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to obtain a film, and nine films were recovered, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. The catalyst of the present invention has high catalytic activity, and the film made of PET obtained by using it is excellent in both thermal stability and heat aging resistance. -110- 1276646 V. DESCRIPTION OF THE INVENTION (Example 9-2) (Synthesis Example of Phosphorus Compound) Synthesis of a phosphorus compound (phosphorus compound B) represented by the following formula (Chem. 45) [Chemical 4 5 ] Q : 〇f \—CH2-P—〇H•一 OC2H5 1. Synthesis of diethyl (1-naphthyl)methylphosphonate under a nitrogen atmosphere at a temperature of 200 ° C (external temperature). 31 g (50 mmol) of triethyl phosphite and 8. A mixture of 83 grams (50 millimoles) of 1-chloromethylnaphthalene was heated to produce a gas (EtCl) until about 30 minutes. After cooling to room temperature, it was obtained. 38 g (75% by weight) of diethyl ether of (1-naphthyl)methylphosphonate as a colorless oily liquid. 'H-NMR (CDCi3, 5): 1. 151(6Hf t), 3. 64K2H, d), 3. 948 (4H. m)t 7. 381-7. 579(4 H, m), 7. 749-7. 867(2H, m), 8. 088-8. 133 (1H, . m) 2. Synthesis of sodium [0-ethyl(1-naphthyl)methylphosphonate] at 6. 5 grams (84 millimoles) of 50% sodium hydroxide and 6. In a mixed solution of 1 ml of methanol, add 6. One milliliter of a solution of 5 g (18 mmol) of (1-naphthyl)methylphosphonic acid diethyl ester in methanol was reflux heated for 24 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was cooled while adding 6. 59 g (63 mmol) of concentrated hydrochloric acid was taken out and precipitated, washed with isopropyl alcohol, and then filtered under reduced pressure. The obtained residue was dissolved in hot isopropyl-111 - 1276646 5. Inventive (110) alcohol, the insoluble matter was taken out, and the isopropyl alcohol was distilled off under reduced pressure, and then the residue was washed with hot η-heptane and dried. 3·8 g (78%) of sodium [0-ethyl(1-naphthyl)methylphosphonate] was obtained. Shape: needle crystal; melting point: 277~281 ° C (decomposition) ^NMR (DMS0-d6, 5): 0. 961 (3H, t, J-7Hz), 3. 223(2H, d), 3. 589(2Hr m), 7. 3 65-7. 468(4H, m. J=7Hz), 7. 651-8. 314(3H( m) „ 3. Synthesis of 0-ethyl(1-naphthyl)methylphosphonic acid (phosphorus compound B) 1 gram in 10 ml with stirring at room temperature (3. 7 millimoles of sodium [0-ethyl (1-naphthyl) methylphosphonate] in an aqueous solution, added 1. 9 g of concentrated hydrochloric acid was stirred for 1 hour. After extracting the reaction mixture, washing the toluene phase with water, and distilling off toluene under reduced pressure, 497 mg (54%) of 0-ethyl(1-naphthyl)methylphosphonic acid was obtained. Shape: colorless oily liquid; ΐ-ΝΜβ (CDC13? δ): 1. 085 (3Η. t, J-7Hz); 3. 450 (2Ht d), 3. 719 (2H, m, 7Hz), 7. 369-7. 532 (4H. m), 7. 727-8. 043(3H, m), 10. . 939 (1H, s) (Polyester polymerization example) The polyester was polymerized in the same manner as in Example 7-1 except that the catalyst was changed. The compound used as a catalyst and the amount added are shown in Table 7. The amount of the aluminum compound added is expressed by the amount of the aluminum atom added to the acid component, and the amount of the phosphorus compound B added is the amount of the phosphorus atom added to the acid component. The IV of the polyethylene terephthalate is up to 0. The polymerization time (AP) required for 65 dl/g is shown in Table 7. -112- 1276646 V. INSTRUCTION DESCRIPTION (111) Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 dl/g of polyethylene terephthalate was exfoliated. The PET resin flakes were used to determine thermal stability parameters (TS) and thermal oxidation stability parameters (TOS). The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to obtain a film, and nine films were recovered, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. The catalyst of the present invention has high catalytic activity, and the film made of PET obtained by using it is excellent in both thermal stability and heat aging resistance. (Comparative Example 7-1) Except that antimony trioxide was used (the amount thereof was added to the ruthenium atom system based on the acid component in PET. 05 Molex%) was carried out in the same manner as in Example 7-1 except that it was used as a catalyst. Antimony trioxide is a commercially available ruthenium (melon) oxide (made by Aldrich Chemicals, Inc., purity 99. 999%). The antimony trioxide used was stirred for about 1 hour to dissolve it in ethylene glycol at 150 ° C to obtain a solution having a concentration of about 1 g/l. The IV of the polyethylene terephthalate reaches 0. The polymerization time (AP) required for 65 dl/g is shown in Table 7. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 d 1 /g of polyethylene terephthalate was exfoliated. The PET resin sheet was used to obtain thermal stability parameters (TS) and thermal oxidation stability parameters (TOS). The results are shown in Table 7. -113- 1276646 V. INSTRUCTION OF THE INVENTION (112) Further, a film was formed by using the above-mentioned PET resin sheet to obtain a film, and nine films were collected, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. Although the catalyst of the present invention has excellent catalytic activity, the thermal stability of the film made of PET obtained by using it is inferior to that of the examples. (Comparative Example 7-2) Except that the phosphorus compound A was further added to the catalyst of Comparative Example 7-1 (the amount of phosphorus added was 0. 03 mol% based on the acid component of PET), This was carried out in the same manner as in Example 7-1. The antimony trioxide is a commercially available antimony (melon) oxide (made by Aldrich Vapor Chemicals Co., Ltd., purity 99. 9 9 9%). The antimony trioxide used was stirred and dissolved in ethylene glycol at 150 ° C to obtain a solution having a concentration of about 10 g / liter. The IV of the polyethylene terephthalate reaches 0. The polymerization time (AP) required for 65 dl/g is shown in Table 7. The change in the catalytic activity of the antimony trioxide cannot be confirmed by the use of the phosphorus compound A. (Comparative Example 7-3) Except for the use of a oxidized pin (the amount of addition is 0. The chromium atom system with respect to the acid component in PET is 0. 03 mol%) was carried out in the same manner as in Example 7-1 except that it was a catalyst. The IV of the polyethylene terephthalate reaches 0. The polymerization time (AP) required for 65 dl / gram is shown in Table 7. Further, according to the conventional method, the IV obtained in the above polycondensation is 0. 65 d 1 /g of polyethylene terephthalate was exfoliated. The thermal stability parameter (TS) and the thermal oxidation stability parameter (TOS) were determined using the PET resin sheet-114- 1276646, and the invention (113) sheet. The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to obtain a film, and nine films were recovered, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. Although the catalyst of the present invention has excellent catalyst activity, the heat stability and heat aging resistance of the film made of PET obtained by using it are inferior to those of the examples. (Comparative Example 7-4). In addition to the use of acetonitrile aluminum (the amount of which is added to the aluminum atom system relative to the acid content of the PET is 0. In the same manner as in Example 7-1, the procedure was carried out in the same manner as in Example 7-1. Although the heating was carried out for more than 150 minutes, the IV of the polyethylene terephthalate could not reach 0. 65 d 1 / gram. (Comparative Example 7-5) Except that lithium acetate dihydrate was used (the amount thereof was added to the lithium atom system based on the acid component in PET. 01 mol%) was carried out in the same manner as in Example 7-1 except that it was used as a catalyst. Although the polymerization was carried out for more than 150 minutes by heating, the IV of polyethylene terephthalate could not reach 0. 6 5 dl / gram. [Table 7] It can be understood from the above examples and comparative examples that when the thermal stability parameter of the PET resin sheet is within the scope of the patent application of the present invention, the film is -115-1276646. The thermal stability will be excellent, and the quality of the film will be excellent; and the quality of the recycled film will be excellent. On the one hand, in the case of the patent application of the present invention, the thermal stability of the film is deteriorated, and the re-use quality of the chip film is also poor. Further, although the catalytic activity of the original aluminum compound and the lithium compound is not good, the activity of the catalyst of the present invention which coexists with the phosphorus compound is excellent, and the obtained polyester is also excellent in thermal stability. On the other hand, when a phosphorus compound is used in combination with a ruthenium compound, the catalytic activity of the ruthenium compound is not affected (Example 8-1) (Preparation of an aqueous solution of a salt-based aluminum acetate) 1 gram of a basic acetic acid Aluminum (hydroxyaluminum diacetate; Aldrich) was added to deionized water in a ratio of 50 ml, and stirred at room temperature for about 12 hours. Thereafter, the liquid temperature was gradually increased while continuing to stir. When the liquid temperature reached about 60 ° C, it was kept at this temperature point for about 2 hours, and the liquid temperature was further raised and the stirring was continued. When the liquid temperature reached about 75 Torr, the temperature was kept stirring at this temperature for about 2 hours or more to obtain a transparent aqueous solution. (Polyester polymerization example) A mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer obtained by a high-purity citric acid and a 2-fold molar amount of ethylene glycol according to a conventional method is added. The aluminum atom is 0% relative to the acid component of the polyester. 035 mol% of the above-mentioned aqueous solution of aluminous aluminum acetate, and 10 g / liter of Irganox 1 425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is 0. 02 Moer % -1 1 6 - 1276646 5. The polycondensation catalyst made of the ethylene glycol solution of the invention (115) was stirred under a nitrogen atmosphere at normal pressure at 245 ° C for 15 minutes. Then, after raising the temperature to 27 5 ° C for 55 minutes, the pressure of the reaction system was slowly lowered to 66. 5 bar (0. 5 Tory), further at 2751, 66. The polymerization reaction was carried out for 5 minutes at 5 bar. The IV and Tm of the obtained PET are shown in Table 8. (Example 8-2) (Preparation of a solution of a salt-based aluminum acetate solution in ethylene glycol) Aluminium acetate (CH3COOAl(OH)2 · 1/3H3B03; Aldrich) was used in ethylene glycol. Stirring was carried out for about 12 hours or more to obtain an ethylene glycol solution having a concentration of about 5 g/liter. (Polyester polymerization example) except that the aluminum atom is 0 with respect to the acid component in the polyester. 035 mol% of the above-mentioned salt-based aluminum acetate glycol solution, and 1 g/l of Irganox 1 425 (Ciba Specialty Chemicals Co., Ltd.) relative to the acid component is 0. The operation was carried out in the same manner as in Example 8.1 except that the ethylene glycol solution was used as a polycondensation catalyst. The IV and Tm of the obtained PET are shown in Table 8. (Comparative Example 8 -1) except that the aluminum atom was 0 with respect to the acid component in the polyester. 03 5 molar % of aluminum acetate (hydroxy aluminum diacetate) of about 10 g / liter of ethylene glycol solution, and 10 g / liter of Irganox 1425 (Ciba Special Chemicals Co., Ltd.) relative In the same manner as in Example 8.1, the ethylene glycol solution having an acid component of 0. 0 2 mol% was used as the polycondensation catalyst. -117-1276646 5. Description of the invention (116) Line operation. The iy and Tm of the obtained PET are shown in Table 8. (Example 8 - 3) (Preparation of a solution of a salt-based aluminum acetate solution in ethylene glycol) A ratio of 1 part by weight of a basic aluminum acetate solution of about 1/16 molar amount of boric acid to 50 ml Add deionized water and stir at room temperature for about 12 hours. Thereafter, the mixture was stirred at about 70 ° C for about 2 hours to obtain a transparent aqueous solution. Ethylene glycol having a capacity ratio of 2 times was added to the aqueous solution, and stirred at room temperature for several hours. Thereafter, the solution was stirred at 100 ° C for several hours, and water was distilled off from the system to obtain an ethylene glycol solution. (Polyester polymerization example) A mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer produced by high-purity p-citric acid and ethylene glycol according to a conventional method is added to the polyester. The acid component has an aluminum atom of 0. 014 mol% of the above-mentioned salt-based aluminum acetate glycol solution, and 10 g/l of Irganox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is 0. The polycondensation catalyst made of 02 mol% of the ethylene glycol solution was stirred for 10 minutes under nitrogen atmosphere at normal pressure at 245 °C. Next, the temperature was raised to 275 ° C for 45 minutes, and the pressure of the reaction system was gradually lowered to 66 · 5 bar (0 · 5 tony), further at 275 ° C, 66. 5 bar was subjected to a polycondensation reaction for 20 minutes to obtain an IV of 0. 38 dl / gram of PET. (Example 8-4) (Preparation of a salt-based aluminum acetate water/ethylene glycol mixed solution) 1 g of a basic aluminum acetate (aluminum diacetate; Aldrich-118-1276646 Inventive Note (117)) Add deionized water to the ratio of 50 halo: liter, and stir at room temperature for about 12 hours. Thereafter, the mixture was stirred at about 70 ° C for about 6 hours to obtain a transparent aqueous solution. Ethylene glycol was added to the aqueous solution in an amount of 3 times (volume ratio) with respect to the aqueous solution, and the mixture was stirred at room temperature for 6 hours to obtain a catalyst solution. (Polyester polymerization example) High-purity citric acid and 2 times the amount of ethylene glycol were placed in a 2-liter autoclave stainless steel autoclave equipped with a stirrer, and added to the acid component was 0. 3 mol% of triethylamine, at 0. Pressurization at 25 Mpa, at 250 ° C, while purifying the water outside the system, and performing an esterification reaction for 11 5 minutes to obtain a bis(2-hydroxyethyl)paraxamate esterified to 95% or more ( A mixture of BHET) and an oligomer (hereinafter, referred to as a BHET mixture). The aluminum atom is added to the BHET mixture relative to the acid component of the polyester. 014% by mole of the above-mentioned salt-based aluminum acetate in water/glycol mixed solution, and 100 g/liter of Irganox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is 0. A polycondensation catalyst made of a 01% molar solution of ethylene glycol was stirred under a nitrogen atmosphere at normal pressure at 25 CTC for 15 minutes. Then, after heating for 60 minutes to 275 t, the pressure of the reaction system was slowly lowered to 66. 5 bar (〇·5 Toli), further at 27 5 ° C, 66. 5 bar was subjected to a polycondensation reaction for 132 minutes, and an IV was obtained. 61 dl/g PET, the present invention is a substance having practical catalyst activity. The obtained PET physical properties are shown in Table 9. (Example 8 - 5) (Preparation example of a solution of a salt-based aluminum acetate in ethylene glycol) -119 - 1276646 5. Description of the invention (118) The above-mentioned salt-based aluminum acetate water/ethylene glycol solution was used. 90~ 1 l〇°C stir for a few hours while distilling off water from the system. As a result, an ethylene glycol solution having a concentration of about 6.5 g/liter was obtained. (Polyester polymerization example) In addition to the addition of the acid component in the polyester, the aluminum atom is 0. 〇14 mol% of the above-mentioned salt-based aluminum acetate glycol solution, and 丨00 g/liter of Irganox 1425 (Ciba Specialty Chemicals Co., Ltd.) relative to the acid component is 0. The polyester was polymerized in the same manner as in Example 8 - 4 except that the polycondensation catalyst made of a molar solution of 0.01% by weight was used. The polymerization time was 133 minutes, and the IV was obtained as 0. 60 dl / gram of PET. The obtained PET physical properties are shown in Table 9. (Examples 8 - 6) (Preparation of a solution of a salt-based aluminum acetate in ethylene glycol) Aluminium acetate (ch3cooai(oh)2 · i/3h3bo3; Aldrich) was used in ethylene glycol. The mixture was stirred at about 70 ° C for 5 hours to obtain a glycol solution having a concentration of about 5 g / liter. (Polyester polymerization example) A mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer produced by high-purity p-citric acid and ethylene glycol according to a conventional method is added to the polyester. The acid component has an aluminum atom of 0. 014 mol% of the above-mentioned salt-based aluminum acetate 5 g/liter ethylene glycol solution, and 1 g/l of Irganox 1425 (Ciba Specialty Chemicals Co., Ltd.) relative to the acid component is 〇 . 聚 1 mol% of the ethylene glycol solution of the polycondensation catalyst, in a nitrogen atmosphere, often -120-1276646 V, invention description (1 19) pressure ' 24 5 ° C, stirring for 1 〇 minutes. Then, the temperature was raised to 275 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 13. 3 bar (0·ι Torri)' further at 27 5 ° C, 13. 3 bar was subjected to a polycondensation reaction for 90 minutes to obtain PET having an IV of 0 · 6 5 d 1 /g. The PET of the obtained PET was 2 equivalent/ton, the Tm was 25 6 ° C, and the L値 was 68. 9, a値 is - 2. 3, b値 is 4 · 2 〇 (Example 8 - 7) (Preparation of ethylene glycol solution of aluminum lactate) Aluminum lactate is prepared into an aqueous solution of about 67 g/liter. Thereafter, ethylene glycol was added at about 10 (TC was heated to distill off water to obtain an ethylene glycol solution of about 29 g/liter. (Polyester polymerization example) In addition to the addition of aluminum relative to the acid component in the polyester The atomic solution is 0. 0 1 4 mol% of the above-mentioned aluminum lactate solution of ethylene lactate, and 1 g/l of Irganox 1 425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is 0. The polyester was polymerized in the same manner as in Example 8 - 4 except that the polycondensation catalyst made of a molar solution of 0.01% by weight was used. The polymerization time was 1 24 minutes, and PET with an IV of 〇 · 6 d 1 /g was obtained. The obtained PET physical properties are shown in Table 9. (Comparative Example 8-2) The aluminum atom was 0 in addition to the acid component in the polyester. 0 1 4 mol% of about 5 g / liter of aluminum lactate in ethylene glycol solution, and 100 g / liter of Irganox 1425 (Ciba Special Chemicals Co., Ltd.) relative to the acid composition is 0. 01 Mo Other than the polycondensation catalyst made of the ethylene glycol solution of the ear % - 121 - 1276646 V. Description of the invention (120) 'The polyester was polymerized in the same manner as in Example 8 - 4. The polymerization time was 168 minutes' and the IV was 0. 61 dl / gram of pet, the catalyst is not active. (Evaluation Results) From the above examples and comparative examples, it is understood that when a solution of dissolved residual acid is used as a catalyst, the polymerization activity is excellent in either case, and the obtained polyester is also A good quality product; in contrast, when a solution in which aluminum carboxylate is not dissolved is used as a catalyst, a result of poor polymerization activity will be obtained. [Table 8] [Table 9] [Field of Industrial Applicability] The possible application range of the polyester of the present invention is, for example, fiber for interior/sleeping represented by fibers for clothing, curtains, carpets, bedding, etc.; Fibers for industrial materials represented by cords, cords, etc.; fibers of various fabrics, various braids, staple fiber non-woven fabrics, long-fiber nonwoven fabrics, packaging films, industrial films, optical films, tape films, photographic films , film for can lamination, film for condensation, film for heat shrinking, gas barrier film, white film, easy-cut film, non-heat-resistant stretch bottle, heat-resistant stretch bottle, direct blow bottle, gas barrier bottle, pressure bottle, heat resistance Various molded articles such as hollow molded bodies such as pressure bottles, mats such as A-PET or C-PET, glass-reinforced polyester, and single-body plastics, and paints or adhesives, etc. -122- 1276646 V. Description of invention (121) 1) Breaking a ^ shaking and ugly _ 屮 屮 N. i. 2) Tree 13 Shake Class 1 § ugly 鄹睁酗 屮芑黥屮咏 | 1 钿屮 ^ fog ·,. Comparative Example 1-1 Example 1-3 Example 2 Example 1-1 Sodium acetate triacetate acetonitrile aluminum phosphate S [11 Μ cold (Ν 卟隳蹯 ^ [Ν |[ > _ Aluminum Irganox 1425 s iii m cold (N隳豸(N >l compound 1 1 0〇U\ to Η-* CM ο * <1 alkali metal content (mole) υ 1 1 ο ^ty 1 soil test metal content (mole) υ 0〇 to to ο ο * <1 Μ (mole) 2) g K) κ> to aluminum content (pprn) On to 〇\ υο LO phosphorus content: (ppm) Os ON ON LO 0 〇 polymerization time / minute X > 〇〇 filtration pressure Rise X D> 〇〇断丝 [姗一]
-123- 1276646 五、發明說明（122) 2)效驟丑_咏_麵^普懲±猶咏騙缅^^/虜w(pp5。 比較例2-2 比較例2-1 實施例2-6 實施例2-5 實施例2-4 實施例2-3 實施例2-2 實施例2-1 _1 醋酸鈉 氯化鋁 醋酸鋰 乙酸乙醯鋁 醋酸鎂 醋酸鋁 醋酸鈉 乙酸乙醯鋁 醋酸鋰 氯化鋁 醋酸鋰 乙酸乙醯鋁 醋酸鈉 i 氯化鋁 醋酸鋰 乙酸乙醯鋁 化合物 0.04 0.0015 0.05 0.02 0.015 0.01 0.025 0.06 0.04 0.015 0.025 0.02 Ο 〇 Ο 〇 to to 1 0.01 ! 0.015 含量/莫耳％ 26.7 to LA Η-* U\ 〇 K5 K-^ LO 1—* 〇 Μ / A1之比値υ ss s »—* \〇 to 4^ 金屬量/ i>pm2) H-* S 〇〇 〇\ v〇 S 〇\ νο 0〇 聚合時間/分 X X t> > [> 〇 〇 〇 濾壓上昇 X X D> t> > 〇 〇 〇 斷絲 【姗2】 -124- 1276646 五、發明說明（123 LO t〇 η- 0 0 0 ^ 翔龉 00 丑難盼鲡51屮«難^繈卧議缅屮^貓_(？？3)。 鄹咏_a 屮¾鄹：t 繈睁觸®+iv_s(ppm)®isal>i(ppm)^tbpf sa^Di>i ( ppm ))®igDJ>w ( ppm )i^rrrrpi。 Φ激缅屮^昤_挪50 ppm。 比較例3-3 比較例3-2 比較例3-1 實施例3-9 實施例3-8 實施例3-7 實施例3-6 實施例3_5 實施例3-4 實施例3-3 實施例3-2 實施例3-1 醋酸鈉 氯化鋁 1磷化合物A SIU躡 冷(N隳 咏爾墦 漤[N >爾 醋酸鈉 三乙酸乙醯鋁 磷酸 |醋酸鋁 Irganox 1425 三氧化銻4> |醋酸鉀 i氯化鋁 磷化合物A 絜h丨蹋 藤N隳 mm (Nil 躍关 ^ IU S (N § W ^ [N =顬 to g»> U\ QU 醋酸鈉 ^zmzjm 磷化合物A SHi^ 泠M® u>mm 豸 IN 11 >躅兴 丨1躡 2 (N隳 §鄹鄯 X 〇J to妙 Crt UU ^ IU® S CN隳 § mm ^ Mil 笈蹯头 ΙΊΠ 1 ^ ：W t [N …圈 盤 化合物 S — g 1 ι—» 1 9""» >~~1 1 鹼金屬含量 _L&pm)_ 1 1 1 g 1 1 1"* Ο 1 1 g ON LA 鹼土金屬含 量（PPm) H-* 〇 OJ L/l g g g ►—» 鋁含量 „(PPm)_ ~A ro b〇 H-» o Lk> U\ On g 磷含量 (ppm)^| g S g § 1~1 o l·—* U\ Ln ON LA Is 〇 On 〇\ LO 〇 to o o kj\ H-* to Μ / A1之比値2) Ο Ο ~λ 16.7 〇 U\ 〇〇 LO 〇 OJ to to 00 1^ U\ to P / Α1之比値3) 1 !〇 Un S . g 〇〇 ON 聚合時間/分 X X X > > > 〇 〇 〇 〇 〇 〇 濾壓上昇 X X X I> I> 0 〇 〇 〇 〇 〇 〇 斷絲 -125- 1276646 五、發明說明（124) 1 )效識丑^絜麵屮 _ ( ppm )faig 额( ppm )ίνΧΊΓΓΓfw。 比較例4-1 實施例4-2 實施例4-1 氯化鋁 醋酸鋰二水合物 ^ g in W ^ ^ \s ® g w II ^ (N 务二 画 □i> ^ 酩 豸 氯化鋁 Irganox 1425 化合物 I 1 to o 鋁含量 (ppm) 1 5； 0〇 磷含量 (ppm) 1 o 〇〇 1 2.9 *-d > >—* ON 聚合時間/分 _ί 〇 1~~k VO 0.01 0.01以下 熱氧化安定性 (T0S) X 〇 〇 濾壓上昇 X 〇 〇 斷絲 tm4〕 -126- 1276646 五、發明說明 (125) 1 )翔顓-&^靡缅^4 ( ppm )^酩缅屮 _ ( ppm )^芹{爾。 比較例5-2 比較例5-1 實施例5-2 實施例5-1 S HI 冷1N n> W 豸(Ν > 爾 靡[II [N n!> W Μ [Ν > 爾 盤 =in S [Ν g 隳 ^ (N ^ 爾 gH> on ίϊά S [II [N 卟 w 豸 [N > 讓 化合物 錦含量 (ppm) _1 — Η—^ Ο ON LO o 磷含量 (ppm) to Ο LO 〇〇 LO LO > 1—1 220 ►—Λ ►—k 1~^ o 聚合時間/分 —— _ — ___1 X X 〇 〇 濾壓上昇 X X 〇 〇 斷絲 -127- 1276646 五、發明說明 (126) 1)絜缅屮苕酩缅屮NMwtb。 比較例6-3 比較例6-2 比較例6-1 實施例6-3 實施例6-2 實施例6-1 三乙酸乙醯鋁 (N □> W Μ (Ν >園 m HI 冷[Ν 豸（Ν >爾 KH IH tS [N | Μ § (Ν S爾 S [II ^ [Ν 卟隳 豸（Ν >爾 S III [N n> m Μ (Ν >圈 化合物 〇 〇 Ο 〇 〇 〇\ 0.014 0.3 0.012 0.04 0.014 o.l O ° 添加量/莫耳％ 1 〇 b〇 21.4 υο LO ι—^ bO VO 添加量比n 120以上 117 110 〇〇 Ό a\ 〇〇 聚合時間/分 5 6〕 -128- 1276646 五、發明說明（127) 比較例7-5 比較例7-4 比較例7-3 比較例7-2 比較例7-1 實施例7-2 實施例7-1 醋酸鋰二水合物 三乙酸乙醯鋁 二氧化锆 三氧化銻 磷化合物A 三氧化銻 錾ill [N n!> m Μ [Ν w 圔 靡職1 u 泠隳（Ν 卧 ® 隳 ^ 11 (Ν 豸 化合物 0.01 0.014 0.03 0.05 1 0.03 〇 0.014 0.03 0.05 0.014 0.01 0.03 添加量/莫耳％ i 150以上 150以上 〇\ 〇〇 〇\ Φ 1 1 0.20 1 〇 to LO Ο 1~1 4^ ο σ\ 1 1 〇 1 0.01以下 Ο Ο 0.01以下 g 00 1 1 X 1 X 〇 〇 薄膜之 熱氧化安定性 1 1 X 1 〇 〇 〇 薄膜之 耐熱老化性 -129· 1276646 五、發明說明（128)-123- 1276646 V. Description of invention (122) 2) Effect ugly _ 咏 _ face ^ general punishment ± 咏 咏 ^ ^ ^ ^ / 虏 w (pp5. Comparative Example 2-2 Comparative Example 2-1 Example 2 6 Examples 2-5 Examples 2-4 Examples 2-3 Examples 2-2 Examples 2-1 _1 Sodium Acetate Aluminum Chloride Acetic Acid Lithium Acetate Acetyl Aluminum Magnesium Acetate Acetate Aluminum Acetate Sodium Acetate Acetate Aluminum Acetate Lithium aluminum chloride, acetic acid, ethyl acetate, sodium acetate, sodium chloride, aluminum chloride, lithium acetate, ethyl acetate, aluminum compound, 0.04, 0.0015, 0.05, 0.02, 0.015, 0.01, 0.025, 0.06, 0.04, 0.015, 0.025, 0.02 Ο 〇Ο 〇 to to 1 0.01 ! 0.015 content/mol % 26.7 To LA Η-* U\ 〇K5 K-^ LO 1—* 〇Μ / A1 ratio ss s »—* \〇to 4^ Metal amount / i>pm2) H-* S 〇〇〇\ v 〇S 〇\ νο 0〇aggregation time/minute XX t>>[> 〇〇〇filter pressure rise XX D>t>> 〇〇〇断丝 [姗2] -124- 1276646 V. Description of invention ( 123 LO t〇η- 0 0 0 ^ 龉 龉 00 ugly 鲡 鲡 51屮 «Difficult ^ 襁 议 屮 屮 猫 猫 猫 猫 猫 猫 猫 猫 猫 猫 猫 猫 猫 猫 + + + + + + + + + + + + + + + + + + Iv_s(ppm)®isal>i(ppm)^tbpf sa^Di>i (ppm ))®i gDJ>w (ppm)i^rrrrpi. Φ 激 屮 昤 昤 挪 挪 50 ppm. Comparative Example 3-3 Comparative Example 3-2 Comparative Example 3-1 Example 3-9 Example 3-8 Example 3-7 Example 3-6 Example 3_5 Example 3-4 Example 3-3 Example 3-2 Example 3-1 Sodium acetate aluminum chloride 1 phosphorus compound A SIU 蹑 cold (N 隳咏 墦漤 [N > sodium acetate triacetate acetonitrile aluminum phosphate | aluminum acetate Irganox 1425 osmium tetroxide 4 > |potassium acetate i aluminum chloride phosphorus compound A 絜h丨蹋藤N隳mm (Nil 跃关^ IU S (N § W ^ [N =顬to g»> U\ QU sodium acetate^zmzjm phosphorus compound A SHi ^ 泠M® u>mm 豸IN 11 >躅兴丨1蹑2 (N隳§鄹鄯X 〇J to wonderful Crt UU ^ IU® S CN隳§ mm ^ Mil 笈蹯头ΙΊΠ 1 ^ :W t [N ... ring compound S — g 1 ι—» 1 9""» >~~1 1 alkali metal content _L&pm)_ 1 1 1 g 1 1 1"* Ο 1 1 g ON LA alkaline earth Metal content (PPm) H-* 〇OJ L/lggg ►—» Aluminium content „(PPm)_ ~A ro b〇H-» o Lk> U\ On g Phosphorus content (ppm)^| g S g § 1 ~1 ol·—* U\ Ln ON LA Is 〇On 〇\ LO 〇to oo kj\ H-* to Μ / A1 ratio )2) Ο Ο ~λ 16.7 〇U\ 〇〇LO 〇OJ to to 00 1^ U\ to P / Α1 ratio )3) 1 !〇Un S . g 〇〇ON polymerization time / minute XXX >>> 〇〇〇〇〇〇 filtration pressure Rise XXX I>I> 0 〇〇〇〇〇〇断丝-125- 1276646 V. Description of invention (124) 1) 丑 絜 絜 絜 ( ( ( ( ppm ) faig amount ( ppm ) ίνΧΊΓΓΓfw. Comparative Example 4 1 Example 4-2 Example 4-1 Lithium aluminum chloride dihydrate ^ g in W ^ ^ \s ® gw II ^ (N wu ji i □ i) 酩豸 Aluminum chloride Irganox 1425 Compound I 1 To o Aluminum content (ppm) 1 5; 0 〇 Phosphorus content (ppm) 1 o 〇〇1 2.9 *-d >>—* ON Polymerization time/minute _ί 〇1~~k VO 0.01 0.01 or less thermal oxidation Stability (T0S) X 〇〇 Filtration pressure rise X 〇〇 broken wire tm4] -126- 1276646 V. Description of invention (125) 1) 颛 颛 - & ^ 靡 ^ ^ 4 (ppm ) ^ 酩 屮 屮 _ ( Ppm )^芹{尔. Comparative Example 5-2 Comparative Example 5-1 Example 5-2 Example 5-1 S HI Cold 1N n> W 豸 (Ν > 尔靡[II [N n!> W Μ [Ν > 盘=in S [Ν g 隳^ (N ^ 尔 gH> on ίϊά S [II [N 卟w 豸[N > Let the compound content (ppm) _1 — Η—^ Ο ON LO o Phosphorus content (ppm) to Ο LO 〇〇LO LO > 1—1 220 ►—Λ ►—k 1~^ o Polymerization time/min – _ — ___1 XX 〇〇 Filtration pressure rise XX 〇〇 Broken wire -127- 1276646 V. Description of invention (126) 1) 絜 屮苕酩 屮苕酩 屮 NMwtb. Comparative Example 6-3 Comparative Example 6-2 Comparative Example 6-1 Example 6-3 Example 6-2 Example 6-1 Aluminum acetate ( N □> W Μ (Ν >园 m HI cold [Ν 豸 (Ν > 尔 KH IH tS [N | Μ § (Ν S 尔 S [II ^ [Ν 卟隳豸 (Ν > er S III [N n> m Μ (Ν > circle compound 〇〇Ο 〇〇〇 \ 0.014 0.3 0.012 0.04 0.014 ol O ° Addition amount / mol % 1 〇b〇21.4 υο LO ι—^ bO VO Addition ratio n 120 Above 117 110 〇〇Ό a\ 〇〇 Polymerization time / minute 5 6] -128- 1276646 V. Description of invention (127) Comparison 7-5 Comparative Example 7-4 Comparative Example 7-3 Comparative Example 7-2 Comparative Example 7-1 Example 7-2 Example 7-1 Lithium acetate dihydrate triacetate acetonitrile aluminum zirconia antimony trioxide Compound A Antimony trioxide ill [N n!> m Μ [Ν w 圔靡 1 1 u 泠隳 (Ν ®® 隳^ 11 (Ν 豸 compound 0.01 0.014 0.03 0.05 1 0.03 〇0.014 0.03 0.05 0.014 0.01 0.03 Add Quantity/mole% i 150 or more 150 or more 〇\ 〇〇〇\ Φ 1 1 0.20 1 〇to LO Ο 1~1 4^ ο σ\ 1 1 〇1 0.01 or less Ο Ο 0.01 or less g 00 1 1 X 1 X Thermal oxidation stability of ruthenium film 1 1 X 1 耐热 film heat aging resistance -129· 1276646 V. Description of invention (128)
比較例8-7 實施例8-5 實施例8-4 乳酸鋁 Irganox 1425 口鼹 § W ^ m 笈驟 ：T鬮 ^ m §漭 ^ m =隳 κ盤 成分 觸媒 乙二醇溶液 乙二醇溶液 水/乙二醇溶液 形狀 0.014 0.01 0.014 0.01 0.014 0.01 添加量 (莫耳％) to 1^ LO 〇〇 H-* LO to Μ φ π> 0.60 0.60 0.61 IV (dl/克） 翔 龉 豸 〇〇 Λ Λ AV (當量/噸） 66.5 66.6 2 VO Pf ^ 1 i—^ 1 to 1 — pf ^ Ο LO 歲cr ㈤ to L/i ON to un as to U\ ON /·—S 〇° '—^ 1— H-^ 〇° ^ w 一 1—* 0〇 1—^ 2 0〇 to 3S 比較例8-1 實施例8-2 實施例8-1 7鬮 ^ m §漭 μ躡 玄骤 b〇 w> L/i rm ^ ·鬮 % mm §隳漭 ^ 躡 s w ^鬮 s iS § F# ^ m s驟 ㈣ 成分 觸媒 乙二醇漿液 乙二醇溶液 水溶液 形狀 0.035 0.02 0.035 0.02 0.035 0.02 添加量 (莫耳％) g 聚合 時間 (分） ο to ο ο IV (dl/克） 激 OO L-ri 〇\ to On S^ ΙΠΚ F$ 【姍00〕 •130-Comparative Example 8-7 Example 8-5 Example 8-4 Aluminum lactate Irganox 1425 鼹 ^ W ^ m 笈 Step: T阄^ m § 漭 ^ m = 隳 盘 disk component catalyst ethylene glycol solution ethylene glycol Solution water/ethylene glycol solution shape 0.014 0.01 0.014 0.01 0.014 0.01 Addition amount (mole%) to 1^ LO 〇〇H-* LO to Μ φ π> 0.60 0.60 0.61 IV (dl/g) Λ Λ AV (equivalent/ton) 66.5 66.6 2 VO Pf ^ 1 i—^ 1 to 1 — pf ^ Ο LO year cr (five) to L/i ON to un as to U\ ON /·—S 〇° '—^ 1—H-^ 〇° ^ w 一 1—* 0〇1—^ 2 0〇to 3S Comparative Example 8-1 Example 8-2 Example 8-1 7阄^ m §漭μ蹑玄骤b〇 w> L/i rm ^ ·阄% mm §隳漭^ 蹑sw ^阄s iS § F# ^ ms (4) Ingredient catalyst ethylene glycol slurry solution of ethylene glycol solution 0.035 0.02 0.035 0.02 0.035 0.02 Addition amount Ear %) g polymerization time (minutes) ο to ο ο IV (dl/g) 激 OO L-ri 〇\ to On S^ ΙΠΚ F$ [姗00] • 130-
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| CN115536823A (en) * | 2022-09-28 | 2022-12-30 | 南京工业大学 | Catalyst for preparing polyester by ring-opening polymerization and method for preparing polyester by using catalyst |
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| CN115536823B (en) * | 2022-09-28 | 2023-10-31 | 南京工业大学 | Catalyst for preparing polyester by ring-opening polymerization and method for preparing polyester by using catalyst |
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