TW581777B - Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin - Google Patents

Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin Download PDF

Info

Publication number
TW581777B
TW581777B TW91121795A TW91121795A TW581777B TW 581777 B TW581777 B TW 581777B TW 91121795 A TW91121795 A TW 91121795A TW 91121795 A TW91121795 A TW 91121795A TW 581777 B TW581777 B TW 581777B
Authority
TW
Taiwan
Prior art keywords
reaction
aromatic
resin
compound component
polyester
Prior art date
Application number
TW91121795A
Other languages
Chinese (zh)
Inventor
Nobuo Minobe
Ryoji Tsukamoto
Tomoyoshi Yamamoto
Tomoyuki Kishino
Kenichi Ishihara
Original Assignee
Teijin Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Ltd filed Critical Teijin Ltd
Application granted granted Critical
Publication of TW581777B publication Critical patent/TW581777B/en

Links

Landscapes

  • Polyesters Or Polycarbonates (AREA)

Abstract

A poly(ethylene aromatic dicarboxylate ester) resin usable for fibers, films or bottle-formed products is produced by polycondensing a diester of an aromatic dicarboxylic acid with ethyleneglycol in the presence of a catalyst system which includes a non-reacted mixture or a reaction product of a titanium compound component (1) including at least one member of titanium alkoxides and reaction products of the titanium alkoxides with aromatic polycarboxylic acid or anhydrides thereof with a phosphorus compound component (2a) including at least one phosphorus compound of the general formula (1) shown below, or a non-reacted mixture of the titanium compound component (1) with a phosphorus compound component (2b) including at least one phosphorus compound of the general formulae (2) and (3) shown below, the contents of titanium and phosphorus atoms in the catalyst system being controlled to satisfy certain requirements.

Description

經濟部智慧財產局員工消費合作社印製 581777 A7 _____ B7_ 五、發明説明（1 ) 技術領域 本發明係有關使用由鈦化合物及磷化合物所得之聚縮 合觸媒，製造聚（芳香族二羧酸乙二酯）樹脂之方法，及 該方法所得之樹脂與其製品。更詳細地說，本發明係有關 使用由鈦化合物及磷化合物所得之聚縮合觸媒，而於製造 過程不會形成（或很少）起因於聚縮合觸媒之異物，故能 製造其有優良透明性、色調及熔融安定性之聚（芳香族二 羧酸乙二酯）樹脂的方法，及所得樹脂與其成形製品，例 如纖維、薄膜及瓶狀成形物等。 背景技術 - 因聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯 二甲酸丙二酯及聚對苯二甲酸丁二酯等聚（芳香族二羧酸 乙二酯）樹脂（以下稱爲聚酯樹脂）具有優良力學特性、 耐熱性、耐候性、耐電絕緣性及耐藥性，故可利用該特性 廣泛使用爲薄膜、纖維或瓶狀形成物等成形品之成形材料 〇 已知製造聚對苯二甲酸乙二酯之方法如，一般係使對 苯二甲酸與乙二醇直接酯化反應，或使對苯二甲酸二酯般 對苯二甲酸之低級烷酯與乙二醇進行酯交換反應，或使對 苯二甲酸與環氧乙烷反應，而生成對苯二甲酸之乙二醇酯 及/或其低聚物後，減壓下將該反應生成物加熱，而進行 一定聚合度之聚縮合反應的方法。 一般製造聚對苯二甲酸乙二酯等聚酯樹脂時，爲了圓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） '- 一 -4- ---，---^---0^------1T------^9— (請先閲讀背面之注意事項再填寫本頁) 581777 A7 B7 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) 滑進行聚縮合反應，而使用聚縮合觸媒。又，聚縮合反應 之速度及所得聚合物之品質深受聚縮合觸媒之種類影響。 已知之聚縮合觸媒如各種金屬化合物，其中，三氧化銻等 銻（St)化合物具有廉價及高聚合活性之特性，且所得 聚合物之色調較佳，而受廣泛使用。但，以s b化合物爲 聚縮合觸媒時，部分的Sb化合物於聚縮合反應中會還原 爲Sb金屬，或生成其他異物，而使所得聚合物發黑及/或 使製造過程不安定化，因此，由所得樹脂製得之成形品會 有品質變差之問題。 特別是以Sb化合物爲聚酯用聚縮合觸媒時，所得聚 酯樹脂經長時間連續熔融紡絲後，噴嘴孔四周會附著堆積 異物（以下單稱：噴嘴異物），而使熔融聚合物流體產生 彎曲現象（彎曲），因此紡絲、延伸過程中會有所得纖維 絲線起毛及/或斷線等問題。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 581777 A7 _____ B7_ V. Description of the Invention (1) Technical Field The present invention relates to the use of polycondensation catalysts obtained from titanium compounds and phosphorus compounds to produce poly (aromatic dicarboxylic acid ethyl Diester) resin method, resin obtained by the method and its products. In more detail, the present invention relates to the use of polycondensation catalysts obtained from titanium compounds and phosphorus compounds, and does not form (or rarely) foreign substances due to polycondensation catalysts in the manufacturing process, so it can be manufactured with excellent properties. Method for poly (aromatic ethylene dicarboxylate) resin of transparency, color tone and melt stability, and the obtained resin and its shaped article, such as fiber, film, and bottle shaped article. Background Art-Poly (aromatic dicarboxylic acid) such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate Resin (hereinafter referred to as polyester resin) has excellent mechanical properties, heat resistance, weather resistance, electrical insulation resistance, and chemical resistance, so it can be widely used as a molding material for molded products such as films, fibers, or bottle-shaped products. 〇 Known methods for producing polyethylene terephthalate are, for example, the direct esterification reaction of terephthalic acid and ethylene glycol, or the lower alkyl esters of terephthalic acid like terephthalic acid and Ethylene glycol is transesterified or terephthalic acid is reacted with ethylene oxide to form ethylene glycol ester and / or its oligomer of terephthalic acid, and the reaction product is heated under reduced pressure. And a method of performing a polycondensation reaction with a certain degree of polymerization. When manufacturing polyester resins such as polyethylene terephthalate, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied for round paper size. '-一 -4- ---, --- ^- --0 ^ ------ 1T ------ ^ 9— (Please read the notes on the back before filling this page) 581777 A7 B7 V. Description of the invention (2) (Please read the notes on the back first (Please fill in this page again for details). Use polycondensation catalyst instead of polycondensation reaction. In addition, the speed of the polycondensation reaction and the quality of the obtained polymer are greatly affected by the type of the polycondensation catalyst. Known polycondensation catalysts such as various metal compounds, among which antimony (St) compounds such as antimony trioxide have the characteristics of low cost and high polymerization activity, and the obtained polymer has better hue and is widely used. However, when the sb compound is used as a polycondensation catalyst, part of the Sb compound will be reduced to Sb metal during the polycondensation reaction, or other foreign substances will be formed, which will cause the resulting polymer to be black and / or cause the manufacturing process to be unstable. There is a problem that the molded product obtained from the obtained resin is of poor quality. Especially when the Sb compound is used as a polycondensation catalyst for polyester, after continuous melting and spinning of the obtained polyester resin, foreign matters (hereinafter referred to as nozzle foreign matters) will accumulate and accumulate around the nozzle hole, thereby melting the polymer fluid. The bending phenomenon (bending) occurs, so that there are problems such as fluffing and / or breaking of the resulting fiber yarn during spinning and drawing.

經濟部智慧財產局員工消費合作社印製 銻化合物以外之聚縮合觸媒提案如，鍺化合物、四-η - 丁氧基鈦等鈦化合物。但，鍺化合物較貴，而有提高 製造聚酯成本之問題。又，以鈦化合物爲聚縮合觸媒時， 雖可抑制所得聚酯樹脂熔融紡絲時，紡絲噴嘴四周產生堆 積異物之現象，但，含有已知之所得聚酯樹脂本身帶黃色 味及/或降低所得聚酯之熔融熱安定性的鈦化合物特有問 題。 爲了解決上述起因於聚縮合觸媒之聚酯樹脂著色問題 ，一般係將鈷化合物加入聚酯中，以抑制黃味著色。添加 鈷化合物確實可改善聚酯色調（顏色b値），但添加鈷化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 B7 五、發明説明（3 ) 合物會降低聚酯之熔融熱安定性，而有促進聚合物分解之 問題。 (請先閱讀背面之注意事項再填寫本頁) 聚酯樹脂之聚縮合觸媒用的其他鈦化合物如，特公昭 48 — 2229號公報，或特公昭47 — 265 97號公報所揭示， 以α -鈦酸爲製造聚酯用觸媒。但，前者之方法中，氫氧 化鈦不易粉末化，後者之方法中，α -鈦酸易變質，故保 存及處理不易，因此工業上不適用，且難得到良好色調（ 顏色b値）之聚合物。 又，特公昭5 9 — 4625 8號公報曾揭示，以鈦化合物及 偏苯三酸反應所得生成物爲製造聚酯用聚縮全觸媒，特開 昭5 8 - 3 8 722號公報曾揭示，以鈦化合物及亞磷酸酯反應 所得之生成物爲製造聚酯用觸媒。使用該聚縮合觸媒時， 雖可某程度提升聚酯之熔融熱安定性，但所得聚酯之色調 (顏色b値）仍不足，故寄望更進一步改善聚酯色調（顏 色b値）。又，不使用銻觸媒爲有效之抑制噴嘴產生異物 的方法，但，不使用銻之方法所得的聚酯及聚酯樹脂製品 ’特別是聚酯纖維之色調仍不足，故目前不含銻之觸媒的 實用性不高。 經濟部智慧財產局員工消費合作社印製 又，已知將回收聚酯樹脂，使用過之聚酯製品（纖維 、薄膜及瓶等）洗淨、粉碎再解聚而得之芳香族二羧酸酯 再生爲原料之方法，但，此時寄望開發出具良好透明性及 色調之再生聚酯的製造方法。 發明揭示 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 ____B7______ 五、發明説明（4 ) (請先閲讀背面之注意事項再填寫本頁) 本發明之目的爲，提供一種能有效率製造不純物含量 較少，具優良透明性及高熔融熱安定性，且色調良好之聚 (芳香族二羧酸乙二酯）樹脂的方法，及所得聚（芳香族 二羧酸乙二酯）樹脂與使用該樹脂而得之各種成形製品。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法係 特徵爲存在含有 (1 )含有鈦烷氧化物、鈦烷氧化物與芳香族多價羧 酸或其酐之反應生成物群中所選出至少1種的鈦化合物成 分，與（2a)含有下列一般式（1 ): .OR2 R】0 -C 一 X —P〈 ( 1 ) II II OR3 ο ο [式中，R1、R2及R3各自獨立爲含1至4個碳原子之烷基 ;X爲—CH2 —基或下列式（la)所示之基： CH—Proposals for polycondensation catalysts other than antimony compounds printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as germanium compounds, titanium compounds such as tetra-n-butoxy titanium. However, germanium compounds are relatively expensive, and there is a problem that the cost of manufacturing polyester is increased. In addition, when a titanium compound is used as a polycondensation catalyst, foreign matter accumulation around the spinning nozzle can be suppressed when the obtained polyester resin is melt-spun, but it contains a known obtained polyester resin with a yellow smell and / or A titanium compound which reduces the heat stability of the obtained polyester is particularly problematic. In order to solve the above-mentioned polyester resin coloring problems caused by polycondensation catalysts, cobalt compounds are generally added to polyesters to suppress yellow taste coloring. The addition of cobalt compounds can indeed improve the color tone of polyester (color b 値), but the size of this paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A7 B7 V. Description of the invention (3) The composition will decrease Melt heat stability of polyester has the problem of promoting polymer decomposition. (Please read the precautions on the reverse side before filling out this page) Other titanium compounds for polyester resin polycondensation catalysts are disclosed in Japanese Patent Publication No. 48-2229 or Japanese Patent Publication No. 47-265 97. -Titanic acid is a catalyst for manufacturing polyester. However, in the former method, titanium hydroxide is not easy to be powdered, and in the latter method, α-titanic acid is easily deteriorated, so it is difficult to store and handle, so it is not industrially applicable, and it is difficult to obtain polymerization with a good hue (color b 之). Thing. Also, Japanese Patent Publication No. 5 9-4625 8 has disclosed that the product obtained by the reaction of a titanium compound and trimellitic acid is a polycondensation catalyst for polyester production. Japanese Patent Publication No. 5 8-3 8 722 has disclosed The product obtained by reacting a titanium compound and a phosphite is a catalyst for manufacturing polyester. When the polycondensation catalyst is used, although the melting heat stability of the polyester can be improved to some extent, the color tone (color b 値) of the obtained polyester is still insufficient, so it is expected that the color tone (color b 値) of the polyester will be further improved. In addition, the use of antimony catalyst is an effective method for suppressing the generation of foreign matter in the nozzle. However, the polyester and polyester resin products obtained by the method without using antimony, especially the color of polyester fibers, are still insufficient. The catalyst is not very practical. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The method of recycling into raw materials, but at this time, it is hoped to develop a method for manufacturing a recycled polyester having good transparency and color tone. The invention reveals that the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A7 ____B7______ 5. Description of the invention (4) (Please read the precautions on the back before filling this page) The purpose of the present invention is to provide a Method for efficiently producing poly (aromatic ethylene dicarboxylate) resin with less impurity content, excellent transparency, high melt heat stability, and good color tone, and the obtained poly (aromatic ethylene dicarboxylic acid) resin Ester) resin and various shaped products obtained by using the resin. The method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention is characterized by the presence of a reaction product group containing (1) a titanium alkoxide, a titanium alkoxide, and an aromatic polyvalent carboxylic acid or an anhydride thereof. At least one titanium compound component selected from (2a) contains the following general formula (1): .OR2 R] 0 -C -X —P <(1) II II OR3 ο ο [wherein R1 and R2 And R3 are each independently an alkyl group having 1 to 4 carbon atoms; X is a —CH2 — group or a group represented by the following formula (la): CH —

經濟部智慧財產局員工消費合作社印製 ]所示至少1種化合物之磷化合物成分的未反應混合物及 反應生成物，及 上述鈦化合物成分（1 )與（2 b )含有下列一般式（2 )及（3 ) ·· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X；297公釐） 581777 A7 B7 五、發明説明（5 (R4 )n —（0)p -P —（0H).II 〇 (2 ) [式中，R4爲含2至18個碳原子之烷基或含6至20個碳 原子之芳基；η爲1或2之整數，又，η爲1時，p爲0 或1之整數，η爲2時，ρ爲0] 0(CH2CH2 -ohnr^ I Η —（0— CH2CH2 ) — 0 —P-ο - (CH2CH2 — 0&gt;ττΗ 0 (3 ) [式中，m、ma及mb各自獨立爲1或2之整數] 所示至少1種磷化合物之磷化合物成分的未反應混合物中 所選出至少1種，且符合下列式（a ) 、 （ b ) 、 （ c )要 件： VII VII 2 1 15/M VI-[P/Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs] Unreacted mixtures and reaction products of phosphorus compound components of at least one compound shown in the above, and the above-mentioned titanium compounds components (1) and (2b) contain the following general formula (2) And (3) ·· This paper size applies to Chinese National Standard (CNS) A4 specifications (210X; 297 mm) 581777 A7 B7 V. Description of the invention (5 (R4) n — (0) p -P — (0H). II 〇 (2) [wherein R4 is an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms; η is an integer of 1 or 2, and when η is 1, p is An integer of 0 or 1, when η is 2, ρ is 0] 0 (CH2CH2 -ohnr ^ I Η — (0— CH2CH2) — 0 —P-ο-(CH2CH2 — 0 &gt; ττΗ 0 (3) [wherein, m, ma, and mb are each independently an integer of 1 or 2] At least one selected from the unreacted mixture of the phosphorus compound components of at least one phosphorus compound shown in the formula, and conforms to the following formulae (a), (b), (c ) Requirements: VII VII 2 1 15 / M VI- [P /

5 Γ -·*· VII (請先閲讀背面之注意事項再填寫本頁) a VII ο 11 VII \1/ P Μ5 Γ-· * · VII (Please read the notes on the back before filling this page) a VII ο 11 VII \ 1 / P Μ

C 經濟部智慧財產局員工消費合作社印製 Μ 中 式 乙 酸 羧 二 族 香莫 芳總 C 之 聚位 對單 量覆 耳重 莫酯 毫二 之乙 素酸 元羧 鈦一一 含 所 系 媒 觸 爲 族 香 芳 中 \)y 酯 C 之 聚位 對單 量覆 耳重 莫酯 毫二 之乙 素酸 元羧 磷二 含族 所香 系芳 媒中 觸 } 爲酯 Ρ 一 一 J Μ 乙値 ， 酸比 値羧的 比二量 的族耳 量香莫 耳芳總 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -8- 581777 A7 _________B7_ 五、發明説明（6 ) 之觸媒系下，使芳香族二羧酸及乙二酯之二酯聚縮合，以 製造聚（芳香族二羧酸乙二酯）。 (請先閱讀背面之注意事項再填寫本頁) 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 包含，利用芳香族二羧酸與乙二醇之二酯化反應製造芳香 族二羧酸及乙二酯之二酯。 又，本發明製造聚（芳香族二羧酸乙二酯）樹脂之方 法中包含，利用芳香族二羧酸之二烷基酯與乙二醇的酯交 換反應製造芳香族二羧酸及乙二酯之二酯。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’芳香族二羧酸之二烷基酯與乙二醇的酯交換反應係於， 至少存在上述觸媒中未反應或反應之鈦化合物成分（1 ) 下進行。 又’該酯交換反應所得含芳香族二羧酸及乙二醇之二 酯的反應混合物可於存在，含有上述至少已含有之未反應 或反應之鈦化合物成分（1)，及上述未反應或反應之磷 化合物成分（2a)，或未反應之磷化合物成分（2b)的觸 媒系下進行聚縮合。 經濟部智慧財產局員工消費合作社印製 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，芳香族二羧酸較佳爲，對苯二甲酸、間苯二甲酸、萘二 甲羧酸、5 —磺基間苯二甲酸金屬鹽及5一磺基間苯二甲 酸鐵鹽中所選出。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，芳香族二羧酸之二烷基酯較佳爲，對苯二甲酸二甲酯、 間苯二甲酸二甲酯、萘二甲酸二甲酯、對苯二甲酸二乙酯 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -9 - 581777 A7 ___ B7 五、發明説明（7 ) 、間苯二甲酸二乙酯及萘二甲酸二乙酯中所選出。 (請先閱讀背面之注意事項再填寫本頁) 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’鈦化合物成分（1 )用鈦烷氧化物較佳爲，下列一般式 (4 ): ΓΓ Ί R5 — 0-一Ti 一 〇——R8 ( 4 ) ^ OR7 人 [式中，R5、R6、R7及R8各自獨立爲含2至10個碳原子 之烷基；me爲1至4之整數] 所示鈦化合物中所選出。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’鈦化合物成分（1 )用芳香族多價羧酸較佳爲，下列一 般式（5 ): fV 剛、 (5) N------ / [式中，〜爲2至4之整數] 經濟部智慧財產局員工消費合作社印製 所示化合物中所選出。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，較佳於0.05至0.2 OMPa加壓下進行酯交換反應。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’供給酯交換反應用芳香族羧酸之二烷基酯較佳爲，對全 莫耳量含有80莫耳％以上之對苯二甲酸二甲酯。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 581777 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（8 ) 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’供給酯交換反應用芳香族羧酸二烷基酯全體之70莫耳 %以上可爲，將聚對苯二甲酸烷二酯解聚後回收的對苯二 甲酸二烷酯。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，該回收之對苯二甲酸二烷酯中2—羥基對苯二甲酸之含 量較佳爲，控制於2ppm以下。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ’觸媒系係由鈦化合物成分（1 )及磷化合物成分（2a ) 或（2b )之未反應混合物構成時，可於酯交換反應開始前 或開始時，將鈦化合物成分（1 )全量加入反應系中，可 於聚縮合反應開始前或開始時，將磷化合物成分（2a)或 (2b)全量加入酯交換反應所得之反應系中。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，觸媒系係由鈦化合物成分（1 )及磷化合物成分（2 a ) 之反應生成物構成時，可於酯交換反應開始前或開始時， 將觸媒全量加入反應系中，又，結束酯交換反應後，可將 所得反應混合物供給聚縮合反應。 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，可於酯交換反應前，將部分鈦化合物成分（1 )，或部 分鈦化合物成分（1 )與磷化合物（2a )之反應生成物， 或部分磷化合物成分（2a)加入反應系中，再於酯以反應 或酯交換反應途中或結束後，及聚縮合反應前或途中至少 1階段中，將殘餘部分加入反應系中。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---*---r---------IT------ (請先閱讀背面之注意事項再填寫本頁) -11 - 581777 A7 B7 五、發明説明（9 ) (請先閲讀背面之注意事項再填寫本頁} 本發明製造聚（芳香族二羧酸乙二酯）樹脂之方法中 ，可於二酯化反應前，將磷化合物成分（2 a )全量加入二 酯化反應系中，或二酯化反應前添加部分磷化合物成分（ 2a)，再於二酯化反應途中或結束後，及聚縮合反應前或 途中至少，階段中，將殘餘部分加入反應系中。 本發明之聚（芳香族二羧酸乙二酯）樹脂爲，由本發 明製造聚（芳香族二羧酸乙二酯）樹脂之方法製得之物。 本發明之聚（芳香族二羧酸乙二酯）樹脂更佳爲，含 有重量％以下之阻胺苯酚系防氧化劑。 本發明之聚（芳香族二羧酸乙二酯）樹脂所含的銻元 素及鍺元素含量較佳爲，各自控制於5/1 000莫耳％以下 〇 本發明之聚酯樹脂爲，含有本發明聚（芳香族二羧酸 乙二酯）樹脂之物。 本發明之聚酯纖維中，聚（芳香族二羧酸乙二酯）樹 脂較佳爲，以聚對苯二甲酸乙二酯爲主成分。 本發明之聚酯薄膜爲，含有本發明聚（芳香族二羧酸 乙二酯）樹脂之物。 經濟部智慈財產局員工消費合作社印製 本發明之聚酯薄膜中，聚（芳香族二羧酸乙二酯）樹 脂較佳爲，以聚對苯二甲酸乙二酯爲主成分。 本發明之瓶狀聚酯成形物爲，含有本發明聚（芳香族 二羧酸乙二酯）樹脂之物。 本發明之瓶狀聚酯成形物中，聚（芳香族二羧酸乙二 酯）樹脂較佳爲，以聚對苯二甲酸乙二酯爲主成分。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 581777 A7 B7 五、發明説明（1〇) 實施發明之最佳形態 (請先閲讀背面之注意事項再填寫本頁) 本發明方法係於存在觸媒下，使芳香族二羧酸及乙二 酉爭之一醋聚縮合’以製造聚（芳香族二殘酸乙二酯）。 本發明方法所使用之觸媒系爲，含有 至少1種選自下述未反應混合物（I )、反應生成物 (II)與未反應生成物（III)者， 未反應混合物（I)爲 (1 )含有鈦烷氧化物、鈦烷氧化物與芳香族多價羧酸或 其酐之反應生成物群中所選出至少一種之鈦化合物成分， 與（2a)含有下列一般式（1): .OR2 矿0-C一 X-P〈 M ) II II X0R3 ⑴ ο ο [式（1)中，R^R2及R3各自獨立爲含1至4個碳原子 之烷基；X爲—CH2—基或下列式（la)所示之基： 一CH一C Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, M Chinese carboxylic acid acetic acid two family fragrant Mofang Total C The polymerization position of a single amount of erythrrolidone diethyl acetate acid carboxytitanium-one contains the media In the family fragrant \) y, the polymerization position of the ester C is related to a single amount of acetonitrile, acetic acid, carboxyphosphine, carboxyphosphorus, and aromatic media. It is an ester P—J Μ acetamidine, acid Bismuth carboxyl is more than the amount of family ears. The amount of fragrant mollar fragrant paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -8- 581777 A7 _________B7_ 5. Catalyst system of invention description (6) Next, poly (condensation of an aromatic dicarboxylic acid and an ethylene diester) is carried out to produce poly (aromatic ethylene dicarboxylic acid). (Please read the notes on the back before filling this page) The method for producing poly (aromatic dicarboxylic acid ethylene glycol) resin according to the present invention includes the use of a diesterization reaction of aromatic dicarboxylic acid and ethylene glycol to produce aromatic Dicarboxylic acids and diesters of ethylene glycol. In addition, the method for producing a poly (aromatic dicarboxylic acid ethylene glycol) resin according to the present invention includes producing an aromatic dicarboxylic acid and ethylene glycol by a transesterification reaction between a dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol. Ester Diester. The transesterification reaction of the dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol in the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention is such that at least the above catalyst is not reacted or reacted. The titanium compound component (1) is performed. Also, the reaction mixture containing the aromatic dicarboxylic acid and the glycol diester obtained by the transesterification reaction may exist, and contain at least the unreacted or reacted titanium compound component (1) already contained above, and the unreacted or Polycondensation is carried out under the catalyst system of the reacted phosphorus compound component (2a) or the unreacted phosphorus compound component (2b). In the method for printing the poly (aromatic ethylene dicarboxylate) resin of the present invention by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the aromatic dicarboxylic acid is preferably terephthalic acid, isophthalic acid, naphthalene Methyl carboxylic acid, 5-sulfoisophthalic acid metal salt, and 5-monosulfoisophthalic acid iron salt are selected. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the dialkyl ester of the aromatic dicarboxylic acid is preferably dimethyl terephthalate, dimethyl isophthalate, naphthalene Dimethyl diformate, diethyl terephthalate This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -9-581777 A7 ___ B7 V. Description of the invention (7), m-phenylene Selected from diethyl formate and diethyl naphthalate. (Please read the precautions on the back before filling this page) In the method for producing poly (aromatic ethylene dicarboxylate) resin according to the present invention, the titanium compound component (1) is preferably a titanium alkoxide. The following general formula (4): ΓΓ Ί R5 — 0-—Ti—10—R8 (4) ^ OR7 [wherein R5, R6, R7, and R8 are each independently an alkyl group containing 2 to 10 carbon atoms; me is Integer 1 to 4] is selected from the titanium compounds shown. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the aromatic polyvalent carboxylic acid for the titanium compound component (1) is preferably the following general formula (5): fV, (5) N ------ / [In the formula, ~ is an integer of 2 to 4] The selected compound is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the transesterification reaction is preferably performed under a pressure of 0.05 to 0.2 OMPa. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the dialkyl ester of the aromatic carboxylic acid used for the transesterification reaction is preferably one containing 80 mol% or more of the total molar amount. Dimethyl phthalate. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 581777 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (8) Poly (aromatic dicarboxylic acid) produced by the present invention In the method of (ethylene glycol) resin, 70 mol% or more of the total amount of the aromatic carboxylic acid dialkyl ester used for the transesterification reaction may be terephthalic acid recovered after depolymerization of polyalkylene terephthalate Dialkyl esters. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the content of 2-hydroxyterephthalic acid in the recovered dialkyl terephthalate is preferably controlled to less than 2 ppm. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, the catalyst system is composed of an unreacted mixture of a titanium compound component (1) and a phosphorus compound component (2a) or (2b). Before or at the beginning of the transesterification reaction, the titanium compound component (1) is added to the reaction system in its entirety. The phosphorus compound component (2a) or (2b) can be added to the transesterification reaction before the polycondensation reaction starts or at the beginning. The response is in. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, when the catalyst system is composed of a reaction product of a titanium compound component (1) and a phosphorus compound component (2a), it can be used in a transesterification reaction. Before or at the beginning, the entire amount of the catalyst is added to the reaction system, and after the transesterification reaction is completed, the obtained reaction mixture can be supplied to the polycondensation reaction. In the method for producing a poly (aromatic ethylene dicarboxylate) resin according to the present invention, before the transesterification reaction, part of the titanium compound component (1), or part of the titanium compound component (1) and the phosphorus compound (2a) The reaction product, or part of the phosphorus compound component (2a), is added to the reaction system, and the remainder is added to the reaction system at least one stage before or during the esterification reaction or transesterification reaction, and before or during the polycondensation reaction. . This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) --- * --- r --------- IT ------ (Please read the precautions on the back before Fill out this page) -11-581777 A7 B7 V. Description of the invention (9) (Please read the precautions on the back before filling out this page} In the method for manufacturing poly (aromatic ethylene dicarboxylate) resin according to the present invention, Before the diesterification reaction, add the phosphorus compound component (2a) to the diesterification reaction system in full, or add a part of the phosphorus compound component (2a) before the diesterification reaction, and then during or after the diesterification reaction, And at least in the stage before or during the polycondensation reaction, the remaining part is added to the reaction system. The poly (aromatic dicarboxylic acid ethylene glycol) resin of the present invention is a poly (aromatic dicarboxylic acid ethylene glycol) resin produced by the present invention. ) Resin prepared by the method. The poly (aromatic dicarboxylic acid ethylene glycol) resin of the present invention is more preferred, and contains amine hindered phenol-based antioxidants in an amount of not more than% by weight. The poly (aromatic dicarboxylic acid) of the present invention The content of antimony element and germanium element in ethylene glycol) resin is preferably controlled to 5/1 000 each Ear% or less. The polyester resin of the present invention is a product containing the poly (aromatic ethylene dicarboxylate) resin of the present invention. Among the polyester fibers of the present invention, the poly (aromatic ethylene dicarboxylate) resin Preferably, it is mainly composed of polyethylene terephthalate. The polyester film of the present invention is a product containing the poly (aromatic dicarboxylic acid ethylene glycol) resin of the present invention. Employees of the Intellectual Property Office of the Ministry of Economic Affairs In the polyester film of the present invention printed by a consumer cooperative, the poly (aromatic dicarboxylic acid ester) resin preferably contains polyethylene terephthalate as a main component. The bottle-shaped polyester molded article of the present invention The poly (aromatic ethylene dicarboxylate) resin of the present invention is preferable. In the bottle-shaped polyester molded product of the present invention, the poly (aromatic ethylene dicarboxylate) resin is preferably a Ethylene phthalate is the main component. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 581777 A7 B7 V. Description of the invention (10) The best form for implementing the invention (please first (Read the notes on the back and fill out this page) Under the catalyst, the aromatic dicarboxylic acid and ethylene diamine are polymerized and condensed to produce poly (aromatic diresidue ethylene glycol). The catalyst used in the method of the present invention contains at least 1 The species is selected from the group consisting of the following unreacted mixture (I), the reaction product (II), and the unreacted product (III). The unreacted mixture (I) is (1) containing a titanyl oxide, a titanyl oxide, and an aromatic compound. At least one titanium compound component selected from the reaction product group of the group polyvalent carboxylic acid or its anhydride, and (2a) contains the following general formula (1): .OR2 ore 0-C-XP <M) II II X0R3 ⑴ ο [In formula (1), R ^ R2 and R3 are each independently an alkyl group having 1 to 4 carbon atoms; X is a —CH 2 — group or a group represented by the following formula (la): —CH—

經濟部智慧財產局員工消費合作社印製 ]所示至少一種化合物之磷化合物成分的未反應混合物， 前述反應生成物（II)爲 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 581777 A7 ____ B7五、發明説明（11 ) 前述鈦化合物成分（1)與前述磷化合物成分（2a)之反 應生成物， 未反應混合物（ΠΙ )爲 鈦化合物成分（1 )與，（2 b )含有下列一般式（2 )或（ 3 ): (R4)n-(〇)p-P~(OH)，II 0 (2) [式（2)中，R4爲含2至18個碳原子之烷基或含6至20 個碳原子之芳基；η爲1或2之整數，又，η爲1時，p 爲〇或1之整數，η爲2時，ρ爲〇] 0 (CH2 CH2 ~ 0 )-,-a Η Η -（0 - CH2 CH2 )b ~ 0 一 卩一〇-（CH2CH2 —Ο Ο (3 ) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 [式（3)中，m、ma及mb各自獨立爲1或2之整數] 所示至少一種磷化合物之磷化合物成分的未反應混合物。 將本發明方法所使用之觸媒系所含的鈦元素及磷元素 含量調整爲，符合下列式（a ) 、（ b )及（c )之要件。 MTl$ 15 (a) 1 ^ ( Mp/Mii )^15 ( b ) 10^ ( Mii + Mp )^100 ( c ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14- 581777 A7 B7 五、發明説明（12 ) 上述式（a) 、 （b)及（c)中，MTi爲，觸媒系所 (請先閱讀背面之注意事項再填寫本頁) 含鈦元素之毫莫耳量對聚（芳香族二羧酸乙二酯）中芳香 族二羧酸乙二酯重覆單位之總莫耳量的比値，Mp爲，觸 媒系所含磷元素之毫莫耳量對聚（芳香族二羧酸乙二酯） 中芳香族二羧酸乙二酯重覆單位之總莫耳量的比値。 又，式（a )中，MTi爲，對應本發明方法中酯交換 反應及聚縮合反應所使用之鈦化合物成分全量的値。MTi 値較佳爲2以上1 5以下，更佳爲3以上1 0以下，特佳爲 3以上6以下。MTi値低於2時，目的物聚酯樹脂之生產 收穫量將不足，且所得聚酯之分子量將不及希望値。又， MTi値超過1 5時，所得聚酯樹脂之熱安定性將不足，且 以高溫對該聚酯樹脂進行成形加工時，會明顯降低分子量 ’而無法得到其有所需機械特性之成形加工製品。 經濟部智慧財產局員工消費合作社印製 式（b )之MTl値同上述，Mp爲，對應本發明方法中 酯交換反應及聚縮合反應所使用之磷化合物成分（2a)或 (2b )全量的値，該Mp/MTi比値較佳爲1以上15以下， 更佳爲2以上1 5以下，特佳爲4以上1 〇以下。Mp/MTi 比値低於1時，所得聚酯帶黃色味，又，超過1 5時，所 得觸媒系於製造聚酯時，聚縮合活性將不足，而難得到具 有所需分子量之聚酯。即，Mp/MTi爲1至15時，可充分 提升所得觸媒系對芳香族二羧酸乙二醇之二酯的聚縮合活 性’而得到具有所需分子量且色調良好之聚酯樹脂。 式（c)中，MTi及Mp之和（MTi + Mp)較佳爲10以 上100以下，更佳爲2〇以上7〇以下。（MTi + Mp)低於 本紙張尺度適用中國國家榡準（CNS ) A4規格（21〇χ297公釐） -15- 581777 A7 B7 五、發明説明（13) (請先閲讀背面之注意事項再填寫本頁) 1 〇時，所得聚酯樹脂之品質均一性及成形加工性將不足 ，例如將所得聚酯樹脂供給靜電施加法，以進行薄膜成形 加工時，其生產收穫率將不足，又，會因所得薄膜之厚度 不均勻，而無法得到充分的薄膜成形加工性及耐衝擊性。 (MTi + Mp )値超過100時，所得聚酯樹脂中會產生起因 於觸媒系之異物，而使透明性不夠。 本發明方法所使用之芳香族二羧酸較佳爲，對苯二甲 酸、間苯二甲酸、萘二甲羧酸、5—磺基間苯二甲酸金屬 鹽及5 —磺基間苯二甲酸_鹽中所選出。 本發明方法中另包含，利用芳香族二羧酸與乙二醇之 二酯化反應製造芳香族二羧酸及乙二醇之二酯的步驟。 該芳香族二羧酸與乙二醇之二酯化反應可於無觸媒或 存在觸媒（例如鹼金屬鹽、鹼土類金屬鹽）下，例如於 0·05至0.20MPa加壓下，或例如23 0至2 8 0 °C溫度之反應 條件下進行。 本發明方法之另一態樣可另包含，利用芳香族二羧酸 之二烷基酯與乙二醇的脂交換反應，製造芳香族二羧酸及 乙二醇之二酯。 經濟部智慈財產局員工消費合作社印製 又，可於存在觸媒下，於160至260 °C溫度，0·05至 0.20ΜΡa加壓下進行芳香族二羧酸之二烷基酯與己二醇的 酯交換反應。 酯交換反應時，壓力低於〇.〇 5 MPa時，以鈦化合物 成分（1)之觸媒作用促進反應將不足，又，超過 0.20MPa時，會大量產生副產物二乙二醇，而使所得聚合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16 - 581777 A7 B7 五、發明説明（14) 物之熱安定性等特性不足。 (請先閲讀背面之注意事項再填寫本頁) 本發明方法使用芳香族二殘酸之二院基醋時，其院基 較佳爲，含1至5個碳原子，更佳爲甲基、乙基或異丙基 等。本發明方法所使用之芳香族二羧酸二烷基酯較佳爲， 對苯二甲酸二甲酯、間苯二甲酸二甲酯、萘二甲酸二甲醋 、對苯二甲酸二乙酯、間苯二甲酸二乙酯及萘二甲苯酸二 乙酯中所選出。 本發明方法中，供給酯交換反應用芳香族羧酸之二烷 基酯可爲對全莫耳量含有80莫耳％以上之對苯二甲酸二 甲酯。 又，供給酯交換反應用芳香族二烷基酯全量之70莫 耳％以上可爲，將聚對苯二甲酸烷二酯解聚後回收的對苯 二甲酸二烷酯。 但，此時回收之對苯二甲酸二烷酯中2—羥基對苯二 甲酸之含量較佳爲，控制於2ppm以下。 經濟部智慧財產局員工消費合作社印製 本發明方法中，利用芳香族二羧酸之二烷基酯與乙二 醇的酯交換反應製造芳香族二羧酸及乙二醇之二酯時，係 於存在觸媒下進行該酯交換反應時，所使用之酯交換反應 用觸媒可爲，本發明方法中所使用之全部或部分聚縮合用 觸媒系。 即，本發明方法係於至少存在上述觸媒中，未與磷化 合物成分（2a)或（2b)反應，或與磷化合物成分（2a) 反應之鈦化合物成分（1 )下，進行芳香族二羧酸之二烷 基酯與乙二醇的酯交換反應後，於存在含有至少已含有未 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 經濟部智慧財產局員工消費合作社印製 581777 A7 B7 --___ 五、發明説明（15 ) 反應或反應後之鈦化合物成分（1 )，及未反應或反應％ 之磷化合物成分（2a)或未反應之磷化合物成分（2b)白勺 觸媒系下，將酯交換反應所得含有芳香族二羧酸及乙二_ 之二酯的反應混合物聚縮合，以製造聚（芳香族二羧酸&amp; 二酯）樹脂。 本發明方法中，構成觸媒系之鈦化合物成分（1丨胃 ，含有鈦烷氧化物、鈦烷氧化物與芳香族多價羧酸或g酉干 之反應生成物群中所選出至少一種之物。 本發明中，構成觸媒系之鈦化合物成分（1 )用_太欠完 氧化物較佳爲，下列一般式（4 ): ίΤ6 Ί R5 -0-一Ti 一 0-一R8 ( 4 ) ^ OR7 [式中，R5、R6、R7及R8各自獨立爲含2至10個碳原子 之烷基及苯基中所選出一種；me爲1至4之整數]所示欽 化合物中所選出。該鈦烷氧化物較佳如，四異丙氧基鈦、 四丙氧基鈦、四- η— 丁氧基鈦、四乙氧基鈦、四苯氧基 鈦、八烷基三鈦酸鹽及六烷基二鈦酸鹽等。 本發明中，構成觸媒系之鈦化合物成分（1 )用芳香 族多價羧酸較佳爲，下列一般式（5 ): 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ---*-------0^------1Τ------^9— 請先閲讀背面之注意事項再填寫本頁) •18- 581777 A7 B7 五、發明説明（16) 〇T_H)na (5) [式中，na爲2至4之整數] 所示化合物中所選出。 該芳香族多價羧酸或其酐更佳如，酞酸、偏苯三酸、 均苯四酸及其酐中所選出。 上述鈦烷氧化物與芳香族多價羧酸（或其酐）進行反 應方式爲，將芳香族多價羧酸或其酐混合於溶劑中，使部 分或全部溶解於溶劑後，將鈦烷氧化物滴入混合液中，再 以0°C至2 00 °C加熱30分鐘以上，更佳爲，以30至15〇 °C加熱40至90分鐘。此時之反應壓力並無特別限制，常 壓即可。又，該溶劑可由能溶解部分或全部芳香族多價羧 酸或其酐之物中作適當選擇，但以乙醇、乙二醇、三甲二 醇、四甲二醇、苯及二甲苯等爲佳。 鈦烷氧化物與芳香族多價羧酸或其酐之反應莫耳比並 無限制。但，鈦烷氧化物比率過高時，會使所得聚酯之色 調變差，及降低軟化點，相反地，鈦烷氧化物比率太低時 ，將難進行聚縮合反應。因此，鈦烷氧化物與芳香族多價 羧酸或其酐之反應莫耳比較佳爲，控制於2/1至2/5。該 反應所得反應生成物可直接供給與上述磷化合物（2a)之 反應，或利用丙酮、甲醇及/或乙酸乙酯等所形成之溶劑 再結晶而精製後，再與磷化合物成分（2a )反應。 本發明方法所使用的觸媒系態樣之一爲，使用鈦化合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) .裝· 訂 經濟部智慧財產局員工消費合作社印製 -19- 581777 A7 B7 五、發明説明（17) (請先閲讀背面之注意事項再填寫本頁) 物成分（1 )與磷化合物成分（2 a )之未反應混合物或反 應生成物。該磷化合物成分（2〇爲，含有上述一般式（ Π所示磷化合物中至少一種。 一般式（1 )所示磷化合物（膦酸酯）較佳如，甲酯 基甲烷膦酸、甲酯基甲烷膦酸、丙酯基甲烷膦酸、丁酯基 甲烷膦酸、甲酯基一膦基一苯基乙酸、乙酯基一膦基-苯 基乙酸、丙酯基-膦基-苯基乙酸及丁酯基-膦基-苯基 乙酸之二甲基酯類、二乙基酯類、二丙基酯類及二丁基酯 類中所選出。 因一般式（1 )所示磷化合物（膦酸酯化合物）對鈦 化合物成分（1)之反應較緩和，因此可拉長聚縮合反應 中鈦化合物之觸媒活性的持續時間，而減少聚酯於聚縮合 反應時所添加之觸媒系添加量。又，合一般式（1 )所示 磷化合物之觸媒系下既使添加多量安定劑，也不會降低所 得聚酯之熱安定性，且無色調不良化。 經濟部智慧財產局員工消費合作社印製 調製鈦化合物成分（1 )與磷化合物成分（2 a )之反 應生成物的方法，混合式（1 )中至少一種之磷化合物所 構成的磷化合物成分（2 a )及溶劑，使部分或全部的磷化 合物成分（2a )溶解於溶劑後，將鈦化合物成分（1 )滴 入混合液，一般再以5 0 °C至2 0 0 t：，較佳爲7 0至1 5 0 °C 加熱反應系1分鐘至4小時，較佳爲30分鐘至2小時。 該反應壓力並無特別限制，可於加壓下10.1至〇.5MPa )， 、常壓下或減壓下（0.001至O.IMPa)進行，又，一般係 於常壓下進行。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20- 581777 A7 B7 五、發明説明（18 ) 上述調製觸媒反應用式（1 )所示磷化合物成分（2 a )時所使用之溶劑可爲，至少能溶解部分磷化合物成分（ (請先閱讀背面之注意事項再填寫本頁) 2 a )之物，並無特別限制，較佳如，乙醇、乙二醇、三甲 二醇、四甲二醇、苯及二甲苯等所選出至少一種所形成之 溶劑，特別爲，同構成最終所得聚酯之二醇成分的化合物 調製觸媒反應中，反應系中鈦化合物成分（1 )與磷 化合物成分（2a )之添加率係設定爲，所得觸媒所含鈦化 合物成分（1)與磷化合物成分（2a)之反應生成物中， 鈦化合物成分（1 )之鈦原子換算莫耳量（mTl )對磷化合 物成分（2a )之磷原子換算莫耳量（mp )的反應莫耳比 mTi/mp 爲 1: 1 至 1: 3，較佳爲 1: 1 至 1: 2。 經濟部智慧財產局g(工消費合作社印製 由反應系利用離心沈澱處理或過濾等方法分離出鈦化 合物成分（1 )與磷化合物成分（2a )之反應生成物後無 需精製，可直接作爲製造聚酯用觸媒，或將分離所得反應 生成物再結晶，例如利用丙酮、甲醇及/或水等再結晶而 精製後，以所得精製作爲觸媒。又，無需由反應系分離出 反應生成物，可直接以含反應生成物之反應混合物作爲含 觸媒混合物。 本發明方法所使用之觸媒系可爲，鈦化合物成分（1 )與磷化合物成分（2 a )之未反應混合物，此時，鈦化合 物成分（1 )與磷化合物成分（2 a )之添加比率較佳爲’ 鈦化合物成分（η之鈦原子換算莫耳量（對磷化合 物成分（2a )之磷原子換算莫耳量（mp )的比mTi/mp爲 -21 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚） 581777 A7 B7 _ 五、發明説明（19 ) 1:1 至 1:15，更佳爲 1:2 至 1:10。 (請先閱讀背面之注意事項再填寫本頁) 本發明方法所使用之觸媒系另一態樣爲，混用鈦化合 物成分（1)與上述一般式（2)及一般式（3)所示磷化 合物中所選出至少一種之磷化合物成分（2 b )。 一般式（2 )所示磷化合物之具體例於p爲〇時’例 如苯基膦酸、甲基膦酸、乙基膦酸、丙基膦酸、異丙基膦 酸、丁基膦酸、甲苯基膦酸、二甲苯基膦酸、聯苯基膦酸 、萘基膦酸、蒽基膦酸、2-羧基苯基膦酸、3-羧基苯基 膦酸、4一羧基苯膦酸、2,3 -二羧基苯基膦酸、2，4 一二 羧基苯基膦酸、2,5 -二羧基苯基膦酸、2,6-二羧基苯基 膦酸、3,4 —二羧基苯基膦酸、3,5 -二羧基苯基膦酸、 2,3,4 —三羧基苯基膦酸、2,3,5 -三羧基苯基膦酸、2,3,6 一三羧基苯基膦酸、2,4,5 -三羧基苯基膦酸、2,4,6-三 羧基苯基膦酸等，其中又以單芳基膦酸爲佳。 經濟部智慧財產局員工消費合作社印製 又，一般式（2 )所示磷化合物之其他具體例於P爲 1時，例如單甲基磷酸酯、單乙基磷酸酯、單三甲基磷酸 酯、單- η- 丁基磷酸酯、單己基磷酸酯、單更基磷酸酯 、單壬基磷酸酯、單癸基磷酸酯、單月桂基磷酸酯、單苯 基磷酸酯、單苄基磷酸酯、單（4-月桂基）苯基磷酸酯 、單（4 一甲基苯基）磷酸酯、單（4 一乙基苯基）磷酸酯 、單（4一丙基苯基）磷酸酯、單（4一（月桂基苯基）磷 酸酯、單甲苯基磷酸酯、單二甲苯基磷酸酯、單聯苯基磷 酸酯、單萘基磷酸酯、單蒽基磷酸酯等。 一般式（3 )所示磷化合物之具體例如，三（羥基乙 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -22- 581777 A7 ___ B7 五、發明説明（2〇) 氧基）磷酸酯、三（羥基乙氧基乙氧基）磷酸酯。 (請先閲讀背面之注意事項再填寫本頁) 本發明方法所使用之觸媒系爲’鈦化合物成分（1) 與磷化合物成分（2b )之未反應混合物時，鈦化合物成分 (1 )之鈦原子換算莫耳量（mTi )對磷化合物成分（2b ) 之隣原子換算莫耳量（mp)的比rriTi/πΐρ較佳爲1: 1至1 :1 5，更佳爲 1 : 2 至 1 ·· 1 0。 含一般式（1 ) 、 （ 2 )及（3 )所示磷化合物之磷化 合物成分（2a )及（2b )，於芳香族二羧酸二烷基酯與乙 二醇之酯交換反應中，既使以與鈦化合物成分（1 )反應 生成物或未反應混合物形態共存，對酯交換反應仍無不良 影響，且於芳香族二羧酸及乙二醇之二酯的聚縮合反應中 ，與鈦化合物成分（1 )具有強觸媒活性。 本發明之聚酯製造方法中，係於存在觸媒下，使芳香 族二羧酸之乙二醇二酯（或其低聚物）所形成之聚合開始 原料聚縮合。 該聚縮合反應較佳爲，以230至320 °C於常壓或減壓 下，又以0.05Pa至0.2 MPa爲佳，或組合前述條件下， 聚縮合15至3 00分鐘。 經濟部智慧財產局員工消費合作社印製 本發明方法所使用之觸媒系係由鈦化合物成分（1 ) 與磷化合物成分（2a)或（2b)之未反應混合物構成時， 可於酯交換反應開始前或開始時，將鈦化合物成分（1 ) 全量加入反應系中，且於聚縮合反應開始前或開始時，將 磷化合物成分（2a)或（2b)全量加入酯交換反應所得之 反應系中。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 581777 A7 B7 五、發明説明（21) (請先閲讀背面之注意事項再填寫本頁) 該觸媒系係由鈦化合物成分（1 )與磷化合物成分（ 2a )之反應生成物構成時，可於酯交換反應開始前或開始 時，將全量加入反應系中，且於結束酯交換反應後，將反 應混合物供給聚縮合反應。 本發明方法中，利用酯交換反應調製芳香族二羧酸之 乙二醇二酯時，可於酯交換反應前，將部分鈦化合物成分 (1)，部分鈦化合物成分（1)與磷化合物成分（2a)之 反應生成物或部分磷化合物成分（2 a )加入反應系中，再 於酯交換反應途中或反應結束後，及聚縮合反應前或途中 至少一階段中，將殘餘部分加入反應系中。 本發明方法中，利用二酯化反應調製芳香族二羧酸之 乙二醇二酯時，可於二酯化反應前，將磷化合物成分（2a )全量或部分磷化合物成分（2a)加入二酯化反應系中， 再於二酯化反應途中或結束後，及聚縮合反應前或途中至 少一階段中，將殘餘部分加入反應系中。 使用上述本發明方法，可得無或極少起因於觸媒系所 形成之異物，且色調良好之聚（芳香族二羧酸乙二酯）樹 經濟部智慧財產局員工消費合作社印製 必要時，本發明之聚酯樹脂可添加反應安定劑，例如 可於製造聚酯時住何階段添加三甲基磷酸酯，又，必要時 可添加一種以上防氧化劑、紫外線吸收劑、難燃劑、螢光 增白劑、平光劑、正色劑、消泡劑及其他添加劑中一種以 上。特別是以聚酯中含有至少含一種阻胺苯酚化合物之防 氧化劑爲佳，該含量較佳爲，對聚酯質量爲1質量％以下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 581777 A 7 B7 五、發明説明（22 ) (請先閱讀背面之注意事項再填寫本頁) 。該含量超過1質量％時，會因防氧化劑本身之熱惡化， 而使所得生成物之品質變差。本發明聚酯所使用之防氧化 劑用阻胺苯酚化合物可爲，季戊四醇一四[3 - （ 3，5 -二 —tert — 丁基—4 —羥基苯基）丙酸酯]、3,9 —雙{2— [3 -(3 — tert — 丁基一 4 一經基一 5 —甲基苯基）丙醯基氧基] —1,1—二甲基乙基}一2,4,8,10 —四噁螺[5,5]i--烷、 1，1,3 —三（2—甲基一4 —羥基—5 — tert— 丁基苯基）丁 烷、1，3,5 — 三甲基一2,4,6 —三（3,5- 二—tert — 丁基—4 —羥基；基）苯、1，3,5-三（4— tert- 丁基一 3 -控基一 2，6 —二甲基苯）間苯二甲酸、三乙二醇一雙[3 — （3 — tert—丁基一5 —甲基一4 —羥基苯基）丙酸酯]、1，6—己 二醇一雙[3 - （3,5 -二一 tert- 丁基一 4一羥基苯基）丙 酸酯、2，2 —硫—二伸乙基—雙[3— (3，5 — 二一 tert— 丁 基一 4 一羥基苯基）丙酸酯]、十八基][3 - （3,5 -二一 tert- 丁基一 4一羥基苯基）丙酸酯]等所選出。又，較佳 爲倂用阻胺苯酚系防氧化劑及硫醚系二次防氧化劑。 經濟部智慧財產局員工消費合作社印製 該阻胺苯酚系防氧化劑加入聚酯之方法並無特別限制 ，較佳於酯交換反應或酯化反應結束後，至聚縮合反應結 束之間任何階段添加。 爲了微調整所得聚酯之色調，於製造聚酯之階段中， 可添加偶氮系、三苯基甲烷系、喹啉系、蒽醌系、酞著系 等有機青色顏料及無機青色顏料中一種以上所形成之正色 劑。當然本發明之製造方法無需使用含降低聚酯之熔融熱 安定性用鈷等無機青色顏料之正色劑。因此，實質上本發 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） •25- 581777 A7 B7_____ 五、發明説明（23 ) 明方法所得之聚酯不含鈷。 (請先閱讀背面之注意事項再填寫本頁) 本發明方法所得之聚酯中，一般利用狩獵型色差計求 得之L値爲80.0以上，b値爲—2.0至5.0。聚酯之L値 低於8 0· 0時，會降低所得聚酯之白色度，而無法得到實 用性高白色度成形物。又，b値低於—2.0時，會減少所 得聚酯之黃味，但會增加青味，b値超過5·0時’會增強 所得聚酯之黃味，因此實用上無法供應製造成形物用。本 發明方法所得之聚酯的L値較佳爲82以上，特佳爲83 以上，b値較佳爲一 1·〇至4.5，特佳爲0·0至0.4。 又，係以下列方法測定本發明方法所得之聚醋的L 値及b値。即，290 °C，真空下將聚酯試料熔融1〇分鐘後 ，將其成形於鋁板上，得厚3.0 :h 1 .0mm之板狀聚酯試驗 片後放入冰水中急冷，再於160 °C下將板狀試驗片乾燥1 小時，其後進行結晶化處理’再將所得板狀試驗片放置於 色差計調整用白色標準板上’利用例如蜜諾塔公司製狩蠟 型色差計CR - 200，測定標準板上之板狀試驗片的表面色 調。 經濟部智慧財產局員工消費合作社印製 本發明之聚酯的固有粘度並無限制’較佳爲〇·5〇至 1.0。該固有粘度範圍下易熔融成形’且可提高所得成形 物之強度。該固有粘度更佳爲0·50至〇.9，特佳爲〇·〇5 至 〇·8。 聚酯之固有粘度的測定方法爲’將供試用聚酯溶解於 原氯苯酚後，3 5 °C下測定。 至於固相聚縮合所得之聚酯多半利用於一般性瓶子等 -26- 本紙張尺度適用中國國家標準（CNS ) A4規格{ 210X 297公釐） 581777 A7 B7 五、發明説明（24 ) ，因此，聚酯中所含固有粘度爲〇 7〇至〇.9()。又，芳香 族一殘酸及乙二醇之酯的環狀三聚物含量較佳爲〇.5wt % 以下，且乙醛含量較佳爲5ppm以下。 (請先閲讀背面之注意事項再填寫本頁) 本發明方法所得之聚（芳香族二羧酸乙二酯）樹脂所 含有的不純物中，鍊元素及鍺元素含量較佳爲，控制於 5/1000莫耳％以下，更佳爲2/1000毫莫耳％。 聚酯所含之銻元素及鍺元素含量超過5/1〇〇〇莫耳％ 時’所得聚酯會產生銻元素特有之發黑現象，又，含鍺元 素會增加所得聚酯之製造成本，而不宜。 爲了將聚（芳香族二殘酸乙二酯）樹脂中銻元素及鍺 元素含量控制於5/1 000莫耳％以下，可控制供應聚縮合 用芳香族二羧酸與乙二醇之二酯所含之銻元素及鍺元素含 量而達成。 又’可由本發明之聚（芳香族二羧酸乙二酯）樹脂製 造聚酯纖維。 此時’聚（芳香族二羧酸乙二酯）樹脂較佳爲，以聚 對苯二甲酸乙二酯爲主成分。 經濟部智慧財產局員工消費合作社印製 又’可由本發明之聚（芳香族二羧酸乙二酯）樹脂製 造聚酯薄膜。 此時，聚（芳香族二羧酸乙二酯）樹脂較佳爲，以聚 對苯二甲酸乙二酯爲主成分。 又，可由本發明之聚（芳香族二羧酸乙二酯）樹脂製 造瓶狀聚酯成形物。 此時，聚（芳香族二羧酸乙二酯）樹脂較佳爲，以聚 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -27- 581777 A7 B7 五、發明説明（25) 對苯二甲酸乙二酯爲主成分。 (請先閱讀背面之注意事項再填寫本頁) 本發明方法之態樣（1 )係於，所使用之聚縮合原料 較佳爲，含80質量％以上，又以85重量％以上爲佳之對 苯二甲酸乙二醇酯的芳香族二羧酸乙二醇酯，且銻元素及 鍺元素之含量限制於5 / 1 000莫耳％以下，利用上述觸媒 系於符合上述要件（a) 、 （b)及（c)之規定下，製造 聚對苯二甲酸乙二酯。該態樣（1 )係利用酯交換反應製 造芳香族二羧酸乙二醇酯，且芳香族二羧酸之烷基中80 莫耳％以上爲對苯二甲酸二甲酯時，係將部分或全部本發 明方法所使用之觸媒系用鈦化合物成分（1 )加入酯交換 反應系中，於〇.〇5至0.20MPa加壓下進行酯交換反應， 再將所得芳香族二羧酸乙二酯供應聚縮合。 經濟部智慧財產局g(工消費合作社印製 該態樣（1 )中，所得聚對苯二甲酸乙二酯樹脂爲， 含有80重量％以上，又以85重量％以上爲佳之聚對苯二 甲酸乙二酯樹脂，又，可混合聚對苯二甲酸乙二酯樹脂以 外之其他樹脂。該聚對苯二甲酸乙二酯樹脂係指，以對苯 二甲酸乙二酯爲主要重覆單位之聚酯。又，該主要重覆單 位係指，全部重覆單位之80莫耳％以上，較佳爲85莫耳 %以上，係由對苯二甲酸乙二酯成分構成。聚對苯二甲酸 乙二酯樹脂爲，與對苯二甲酸乙二酯成分以外之第3成分 共聚合之物時，第3成分（共聚成分）如，2,6 -萘二羧 酸、間苯二甲酸、酞酸等對苯二甲酸以外之芳香族二羧酸 ;己二酸、壬二酸、癸二酸、癸二羧酸等脂肪族二羧酸； 環己烷二羧酸等脂環族二羧酸。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 581777 A 7 B7 五、發明説明（26 ) (請先閱讀背面之注意事項再填寫本頁) 該態樣（1 )之聚酯樹脂的固有粘度（〇 -氯苯酚，3 5 °C)較佳爲0.50至0.80，更佳爲〇·55至0.75，特佳爲 0.60 至 0.70。 將態樣（1 )聚對苯二甲酸乙二酯樹脂例如使用於薄 膜成形用時，爲了提升處理性，可含有滑劑用平均粒徑 0 · 0 5至5 · 0 &quot; m之不活性粒子0 · 0 5至5 · 0重量％。此時， 本發明之聚對苯二甲酸乙二酯樹脂爲了維持高透明性之特 性，所添加之不活性粒子粒徑愈小愈佳，又，其添加量愈 少愈好。溶劑用不活性粒子如，膠體二氧化矽、多孔質二 氧化矽、氧化鈦、碳酸鈣、磷酸鈣、硫酸鋇、氧化鋁、氧 化銷、高嶺土、複合氧化物粒子、交聯聚苯乙烯、丙烯系 交聯粒子、甲基丙烯系交聯粒子、聚矽氧烷粒子等。又， 將對苯二甲酸乙二酯樹脂使用於薄膜、纖維、瓶等各種成 形品時，必要時可含有防氧化劑、熱安定劑、粘度調整劑 、可塑劑、色相改良劑、核劑、紫外線吸收劑等各種機能 劑。 經濟部智慧財產局8工消費合作社印製 本發明之態樣（2 )爲，使用鈦化合物成分（1 )與磷 化合物成分（2a )之未反應混合物或反應生成物所構成的 觸媒系，利用對苯二甲酸烷基二酯，較佳爲對苯二甲酸二 甲酯，與乙二醇之酯交換反應（壓力：0.05至0.20MPa) 調製對苯二甲酸及乙二醇之二酯，再聚縮合，以製造聚對 苯二甲酸乙二酯樹脂。此時，需將觸媒系組成控制爲，符 合上述要件（a) 、 （b)及（c)。其後由該聚對苯二甲 酸乙二酯樹脂製造聚酯纖維。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -29- 581777 Α7 Β7 五、發明説明（27) (請先閱讀背面之注意事項再填寫本頁) 該聚酯樹脂之固有粘度較佳爲0.40至0.80，更佳爲 0.45至0.75，特佳爲0.50至0.70。固有粘度低於0.40時 ，纖維強度將不足而不宜，又，超過0.80時，會造成原 料聚合物之固有粘度過剩，而不符經濟效益。 本發明方法之態樣（2 )中，製造聚酯纖維之方法並 無特別限制，可使用目前已知之聚酯熔融紡絲法，較佳如 ，以270 °C至300 °C將聚酯熔融後，以400至5000 m/分之 熔融紡絲速度紡絲。該紡絲速度範圍下，可得充分纖維強 度，且可安定捲取。又，捲取聚酯纖維後再延伸，或無需 捲取下連續性進行延伸處理，均可得延伸絲。爲了使本發 明之聚酯纖維具有柔軟觸感，可進行鹼減量處理。 上述製造聚酯纖維時，紡絲用噴嘴之形狀並無限制， 可爲Η形或非Η形’又’可爲中空纖維用結絲口。 經濟部智慧財產局員工消費合作社印製 本發明之態樣（3 )爲，存在二醇溶劑中使一般式（4 )所示鈦院氧化物所形成之鈦化合物成分，與式（1 )所 示磷化合物所形成之磷化合物成分加熱反應，而得之反應 生成物所構成的聚縮合觸媒系下，將例如高純度對苯二甲 甲酸與乙二醇之酯化反應所製得的芳香族二羧酸，例如對 苯二甲酸與乙二醇之二酯或其低聚物供給聚縮合反應，以 進行聚縮合，而製造聚（芳香族二羧酸乙二酯）樹脂。其 後將該聚（芳香族二羧酸乙二酯）樹脂供給薄膜成形步驟 ，得聚酯薄膜。 該態樣（3 )中，所使用之觸媒系所含的磷原子對鈦 原子之莫耳比較佳爲，1·〇以上低於8.0，更佳爲2.0以上 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐） •30- 581777 A7 B7___ 五、發明説明（28 ) 低於7.0。 (請先閱讀背面之注意事項再填寫本頁) 反應生成物中混有未反應之鈦化合物成分（1 )時’ 所得聚酯樹脂色調將不足’又’反應生成物中混有未反應 之磷化合物成分（2a)時，會阻礙對苯二甲酸之乙二醇酯 的聚縮合反應。 又，鈦化合物成分（1 )與磷化合物成分（2 a )之反 應方法爲，混合鈦化合物成分（1 )、磷化合物成分（2 a )及二醇溶劑後，將混合物加熱。反應生成物一般係以溶 液狀態存在。爲了均勻進行該反應’又以分別調製鈦化合 物成分（1 )及磷化合物成分（2a )之二醇溶劑溶液後， 混合再加熱之方法特佳。又，反應溫度爲常溫時，反應將 不足，而有反應所需時間過長之問題，因此，爲了均勻且 有效率得到反應生成物，反應溫度較佳爲50至2001：， 反應時間較佳爲1分鐘至4小時。具體之反應溫度如，所 使用之二醇爲乙二醇時較佳爲100 °C至200 °C，又，反應 時間更佳爲3 0分鐘至2小時。 該態樣（3 )所使用之觸媒系較佳爲，符合上述要件 (a) 、 （b)及（c) 〇 經濟部智慧財產局員工消費合作社印製 製造態樣（3 )之聚酯薄膜的方法可爲，將聚（芳香 族二羧酸乙二酯）樹脂熔融擠押再急冷，得未延伸薄膜後 ，將該未延伸薄膜雙軸延伸。又，延伸處理後，必要時可 進行熱固定處理及弛緩熱處理。 所使用之芳香族二羧酸如，對苯二甲酸、酞酸、間苯 二甲酸、萘二羧酸、二苯基二羧酸、二苯氧基乙烷二殘 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - 581777 Α7 Β7 五、發明説明（29 ) 或其酯形成性衍生物。 (請先閱讀背面之注意事項再填寫本頁) 該方香ί矢一殘酸可倂用少量己二酸、壬二酸、癸二酸 、癸烷二羧酸等脂肪族二羧酸；環己烷二羧酸等脂環族二 殘酸，又’其可爲酯形成性衍生物。另外，乙二醇可倂用 少量（！ 〇莫耳％以下）三甲二醇、丙二醇、四甲二醇、新 戊二醇、己烷甲二醇、十二甲二醇、環己烷二甲醇等脂環 族一醇，雙酣、氬酉昆、2，2—雙（4 一 /5 —羥基乙氧基苯基 )丙烷類等芳香族二醇。 又’可共用芳香族二殘酸及少量（1莫耳％以下）均 苯三酸、三羥甲基乙烷、三羥甲基丙烷、三羥甲基甲院、 季戊四醇等多官能性化合物。 經濟部智慧財產局員工消費合作社印製 構成態樣（3 )之聚酯薄膜用聚酯較佳爲，對苯二甲 酸或其酯形成性衍生物對芳香族二羧酸1 〇 〇莫耳％之使用 量爲80莫耳％以上，又以90莫耳％以上爲佳，乙二醇或 其酯成形性衍生物對脂肪族二醇1 0 0莫耳％之使用量爲8 0 莫耳％以上，又以90莫耳％以上爲佳之聚對苯二甲酸乙二 酯。特別是以原料用全部二羧酸成分之8 0莫耳％以上爲 對苯二甲酸，經酯化反應而得之聚對苯二甲酸乙二酯爲佳 。比較以對苯二甲酸二甲酯爲原料之聚對苯二甲酸乙二酯 ，以對苯二甲酸爲原料物質之聚對苯二甲酸乙二酯無需酯 交換反應觸媒，因此無需添加酯交換反應觸媒失活用安定 劑。故具有能抑制安定劑用磷化合物與鈦化合物之間所產 生的相互作用，而減少鈦化合物添加量之優點。 下面將詳述經由酯化反應製造聚酯之方法。 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇χ297公釐） -32- 581777 A7 _ _B7 五、發明説明（3〇) (酯化步驟） (請先閱讀背面之注意事項再填寫本頁) 製造聚酯時，首先將芳香族二羧酸及脂肪族二醇酯化 。具體而言即，調製含芳香族二羧酸及脂肪族二醇之漿液 。該漿液中，對芳香族二羧酸1莫耳之脂肪族二醇含量一 般爲1.1至1.6莫耳，較佳爲1.2至1.4莫耳。其後將該 漿液連續供給酯化反應步驟。 進行酯化反應較佳於，反應物自己循環過程中於一階 段進行，或直列鏈結2個以上酯化反應基時進行，又，均 於脂肪族二醇回流之條件下，利用精餾塔將反應所生成之 水排出系外。 反應物自己循環過程中連續於一階段進行酯化時，一 般係於反應溫度爲240至2 8 0 °C，又以2 5 0至270°C爲佳 ，反應壓力爲常壓至0.3 MPa之反應條件下進行，又，一 般係反應至酯化率爲90 %以上，又以95 %以上爲佳。 經酯化步驟，可得芳香族二羧酸與脂肪族二醇之酯化 反應物（低聚物），該低聚物之聚合度較佳爲4至1 0。 其後將所得低聚物供給下列聚縮合步驟。 經濟部智慧財產局員工消費合作社印製 (聚縮合步驟） 聚縮合觸媒係於存在上述聚縮合觸媒系且減壓下，以 聚酯熔點以上之溫度（一般爲240至280 °C )，將酯化步 驟所得之低聚物加熱而聚縮合。又，聚縮合反應中，未反 應之脂肪族二醇及聚縮合所產生之脂肪族二醇較佳係餾去 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇'〆297公釐） -33- 581777 A7 B7 五、發明説明（31 ) 反應系外。 (請先閲讀背面之注意事項再填寫本頁) 聚縮合反應可單槽進行，或分成複數個槽進行。例如 ，以二階段進行聚縮合反應時，第1槽之聚縮合反應係於 反應溫度24 5至290°C，又以260至2 8 0 °C爲佳，反應壓 力100至lkPa，又以50至2kPa爲佳之條件下進行，最 終第2槽之聚縮合反應係於反應溫度265至3 00 °C，又以 270至290 1：爲佳，反應壓力1000至10Pa，又以500至 3〇Pa爲佳之條件下進行。 如此可製得構成聚酯薄膜用聚酯，又，一般所得聚酯 爲，以熔融狀態擠出再冷卻之粒狀（條狀）物。此時，所 得聚酯之極限粘度（以下稱爲IV )爲0.40至0.80dl/g， 較佳爲 0.50 至 0.70dl/g。 本發明之聚酯薄膜可爲單層或雙層以上之層合薄膜。 又，層合薄膜可爲，單層以上爲本發明之聚酯薄膜所形成 之層，但以全部爲本發明之聚酯薄膜所形成層爲佳。 經濟部智慧財產局員工消費合作社印製 薄膜成形時之延伸條件等製造條件可依目的物薄膜之 表面特性、密度、熱收縮率等物性，作適當選擇。例如， 以[Tg — 10]至[Tg + 6 0]°c之溫度（其中，Tg :聚酯之玻璃 化溫度），將未延伸薄膜之單軸方向（縱方向或橫方向） 延伸2.5倍以上，又以3倍以上爲佳，再以Tg至[Tg + 30] °C之溫度，將垂直於前延伸方向之方向延伸爲2.5倍以上 ，又以3倍以上爲佳。又，必要時可再度延伸縱方向及/ 或橫方向。縱方向延伸倍率乘橫方向延伸倍率而得之面積 延伸倍率較佳爲9倍以上，更佳爲1 2至3 5倍，特佳爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34- 581777 A7 B7 五、發明説明（32 ) (請先閲讀背面之注意事項再填寫本頁) 1 5至3 0倍。延伸處理後，可進行熱固定處理，又，必要 時熱固定處理前或後，可進行弛緩處理。熱固定處理之溫 度較佳爲，[Tg + 70]至[Tm — 10]。(：（其中，Tm:聚酯熔點 )，例如180至25 0°C，熱固定時間較佳爲1至60秒。 本發明之聚酯薄膜爲了提升處理性，可添加滑劑用平 均粒徑0 · 0 5至5 · 0 // m之不活性粒子〇 · 〇 5至5.0重量0/〇。 所添加之不活性粒子如上述之膠體二氧化矽、多孔質二氧 化矽、氧化鈦、碳酸鈣、磷酸鈣、硫酸鋇、氧化鋁、氧化 鉻、高嶺土、複合氧化粒子、交聯聚苯乙烯、丙烯系交聯 粒子、甲基丙烯系交聯粒子、聚矽氧烷粒子等。 本發明之態樣（4)爲’存在上述觸媒系下，使芳香 族二羧酸之二烷基酯與乙二醇進行酯交換反應，再聚縮合 ’以製造聚酯樹脂時，該芳香族二羧酸之二烷基酯的70 重量％部分係使用，將聚對苯二甲酸烷二酯解聚再回收之 對苯二甲酸二甲酯。又，此時之觸媒系較佳係調製爲，符 合上述要件（a) 、（b)及（c)。 經濟部智慧財產局員工消費合作社印製 該態樣（4 )中，供解聚用之聚對苯二甲酸烷二酯較 佳爲聚對苯二甲酸乙二酯，特佳爲，回收之瓶子、回收之 聚酯纖維製品、回收之聚酯薄膜製品及該製品製造過程中 所產生之聚合物屑等回收之聚酯。將聚對苯二甲酸烷二酯 解聚而得之對苯二甲酸二甲酯低於7〇重量％時，最終所 得之聚酯或聚酯纖維中所含之成分內，來自回收之對苯二 甲酸二甲酯成分的比率會降至50%，而減弱環境柔性製品 之印象而不宜。將聚對苯二甲酸烷二酯解聚而得之對苯二 -35- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 一_____B7 五、發明説明（33 ) 甲酸二甲醋較佳爲80重量％以上，更佳爲9〇重量％以上 〇 本發明所抹用之將聚對苯二甲酸烷二酯解聚以製造對 苯二甲酸二甲醋的方法並無特別限制，例如，以乙二醇將 聚對苯二甲酸烷二酯解聚後，以甲醇進行酯交換反應，再 將所得聚對本一甲酸二甲酯再結晶或蒸餾而精製化之方法 。將聚對苯一甲酸烷二酯解聚而得之對苯二甲酸二甲酯所 含不純物中，2 —羥基對苯二甲酸含量較佳爲2ρρηι以下 〇 上述方法所製得之聚酯可使用於製造纖維、薄膜、瓶 等。製造纖維之方法可同態樣（2 )所記載之方法，製造 薄膜可使用態樣（3 )所記載之方法。 本發明之態樣（5 )爲，利用本發明方法製造聚對苯 二甲酸乙二酯薄膜。此時所使用之原料用對苯二甲酸（ T A )爲，將所含不純物之含量控制於對苯二甲酸單甲酯 (MMT)含量：lOOOppm以下；4一羧基苯甲醛（4— CBA )、對甲苯酸（P— TA)、安息香酸（BA )及羥基對苯二 甲酸二甲酯（HDT)之合計含量：1 ppm以下。該對苯二 甲酸可爲，於烷二醇中，將使用過之聚酯包裝材料加熱解 聚後，利用甲醇對解聚生成物進行酯交換反應處理，再將 所得對苯二甲酸二甲酯（DMT )加水分解而得之物。又， 所使用之聚縮合觸媒爲，一般式（4 )所示鈦烷氧化物與 一般式（1 )所示磷化合物之反應生成物，且觸媒中所含 磷原子之莫耳量與鈦原子之莫耳量的比値較佳爲1 . 〇以上 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ------1---— (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產笱員工消費合作社印製 -36- 經濟部智慧財產局員工消費合作社印製 581777 A7 B7____ 五、發明説明（34 ) 低於8.0。 該態樣（5 )中，爲了得到MMT含量爲lOOOppm以 下之對苯二甲酸，D Μ T之加水分解反應較佳於溫度2 3 〇 至260°C，壓力3.0至4.6MPa (表壓）下進彳7 ’更佳爲溫 度250至260。(：，壓力4.0至4.6MPa (表壓）下處理2至 3小時。又，加水分解反應所生成之Me0H可以將汽提用 蒸氣導入反應器之方法，連同副產物二甲基醚一起去除。 將加水分解反應所生成之TA懸浮或溶解於水中’再 由反應器排出，其後經複數次結晶處理，再以固液分離法 捕集。將所得TA餅乾燥、粉碎而漿化後’將其供給酯化 反應及聚縮合反應。 上述方法所得之對苯二甲酸的MMT含量爲1 000ppm 以下，且4— CBA、ρ— ΤΑ、BA及HDT之合計含量爲 1 ppm以下，故適用爲薄膜用聚酯。 TA所含MMT低於l〇〇〇ppm時，可使聚縮合反應所 得之聚對苯二甲酸乙二酯的二醇末端封鏈，而提升熱安定 性，又，超過1 OOOppm時，會降低所得聚對苯二甲酸乙 二酯之透明性。 該態樣（5 )之聚對苯二甲酸乙二酯樹脂較佳爲’全 部酸成分基準下，TA成分佔有率爲85莫耳％以上’全部 二醇成分基準下，乙二醇成分佔有率爲85莫耳°/。以上。 態樣（5 )之聚對苯二甲酸乙二酯聚酯樹脂可含有合 計量1 5莫耳％以下之聚對苯二甲酸乙二酯以外的聚（芳 香族二羧酸烷二酯）樹脂，其中，酸成分可爲，2,6 -萘 ---.---r---9------IT------φ— (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -37- 581777 A7 B7___ 五、發明説明（35 ) (請先閱讀背面之注意事項再填寫本頁) 二羧酸、2，7—萘二羧酸、1,5-萘二羧酸、1,7-萘二羧酸 、其他萘二羧酸之異構物、間苯二甲酸、二苯基二羧酸、 二苯氧基乙烷二羧酸、二苯基醚二羧酸、二苯基碾二羧酸 等芳香族二羧酸成分；六氫對苯二甲酸、六氫間苯二甲酸 等脂環式二羧酸；己二酸、壬二酸、癸二酸等脂肪族二羧 酸成分；p-yS —羥基乙氧基安息香酸、6 -羥基己酸等 含氧酸等之二官能性羧酸成分中所選出’又，乙二醇以外 之二醇成分可爲’三甲二醇、四甲二醇、六甲二醇、十甲 二醇、新戊二醇、二乙二醇、1,1 一環己烷二甲醇、1，4一 瓖己烷二甲醇、2，2—雙（4’一 yS —羥基苯基）丙烷、雙 (4’一 Θ —羥基乙氧基苯基）硕等所選出至少一種以上， 另外，可與1 〇%以下之官能以上多官能化合物共聚合。 將態樣（5 )中上述方法所得之聚酯樹脂熔融擠押再 急冷，而得未延伸薄膜後’將該未延伸薄膜雙軸延伸，可 得延伸聚薄膜。又，延伸處理後，必要時可對該薄膜進行 熱固定處理及/或弛緩熱處理。 經濟部智慧財產局員工消費合作社印製 本發明之態樣（6 )爲，存在部分上述觸媒系下，對 使用過之聚酯材料經解聚、酯交換處理、加水分解處理而 回收之對苯二甲酸二甲酯，及含量爲70重量％之芳香族 二羧酸烷酯、乙二醇進行酯交換處理後，對下一反應系追 加觸媒系殘餘部分，而使酯交換反應所得之酯或其低聚物 聚縮合，再由所得聚酯樹脂製造聚酯薄膜。此時所使用之 觸媒系爲，鈦化合物成分（1 )與磷化合物成分（2a )之 混合物，又，酯交換反應所使用之觸媒爲鈦化合物成分（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -38- 581777 A7 B7 五、發明説明（36 ) (請先閱讀背面之注意事項再填寫本頁) 1 )，所得酯或低聚物之聚縮合反應時再添加磷化合物成 分（2a )。該觸媒系較佳爲，符合上述要件（a ) 、（ b ) 及（c )。所得聚酯樹脂中，對苯二甲酸乙二酯重覆單位 之含量對全部重覆單位量較佳爲80莫耳％以上。聚酯樹 脂中非對苯二甲酸乙二酯重覆單位之二羧酸成分及二醇成 分可各自爲態樣（5 )所記載之物。 該態樣（6 )之製造方法中，以聚對苯二甲酸烷二酯 解聚而得之對苯二甲酸二甲酯爲聚酯原料中芳香族二羧酸 之二烷基酯用時，其含量較佳爲，構成聚酯用全部酸成分 之5 0莫耳。/。以上。 該聚對苯二甲酸烷二酯較佳爲聚對苯二甲酸乙二酯， 特佳爲回收之PET瓶、回收之聚酯纖維製品、回收之聚 酯薄膜製品及該製品之製造過程所產生之聚合物屑等回收 之聚酯。 經濟部智慧財產局8工消費合作社印製 將聚對苯二甲酸烷二酯解聚而得之對苯二甲酸二甲酯 含量低於70質量％時，會因最終所得之聚酯，或聚酯薄 膜所含成分內來自對苯二甲酸二甲酯之成分的比率降至 5〇% ’而使用過之聚酯製品的再利用效率不足。又，將聚 對苯二甲酸烷二酯解聚而得之對苯二甲酸二甲酯，對全部 芳香族二羧酸二烷基酯之全量的含量較佳爲80重量％以 上，更佳爲90重量％以上。 使用再生而得之對苯二甲酸二甲酯時，其製造方法無 特別限制，例如可爲，以乙二醇將聚對苯二甲酸乙二酯解 聚後’以甲醇進行酯交換，再將所得對苯二甲酸二甲酯再 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） -39· 581777 A7 B7 五、發明説明（37) (請先閱讀背面之注意事項再填寫本頁) 結晶或蒸餾而精製化之方法。將聚對苯二甲酸酯解聚而得 之對苯二甲酸二甲酯中，不純物之2—羥基對苯二甲酸含 量較佳爲2ppm以下。 聚酯薄膜所使用之聚酯的固有粘度較佳爲0.50至 〇·80更佳爲0·55至0.75，特佳爲0.60至0.70。固有粘度 爲該範圍時，可得充分薄膜強度，且無需過度提升原料聚 合物之固有粘度，而符合經濟效益。 又，該聚酯薄膜之製造方法並無特定限制，可將聚酯 樹脂熔融擠押再急冷，而得未延伸薄膜後，將該未延伸薄 膜雙軸延伸而得。又，延伸處理後，必要時可進行熱固定 處理及/或弛緩熱處理。 本發明之態樣（7 )爲，製造以對苯二甲酸乙二酯構 造爲主要重覆單位之聚酯樹脂時，所使用之觸媒系爲，鈦 化合物成分（1 )與一般式（2 )或（3 )所示磷化合物中 至少一種所形成之磷化合物成分（2b )的混合物，該鈦化 合物成分（1 )所使用之鈦烷氧化物較佳爲，一般式（4 ) 所示化合物中所選出。又，該態樣（7 )所使用之觸媒系 較佳爲，符合上述要件（a ) 、（ b )及（c )。 經濟部智慧財產局員工消費合作社印製 態樣（7 )中，對苯二甲酸之乙二醇酯或其低聚物較 佳爲，由對苯二甲酸二烷基酯與乙二醇之酯交換反應製得 ，又，該對苯二甲酸二烷基酯較佳爲對苯二甲酸二甲酯。 供給該酯交換反應之部分或全部對苯二甲酸二甲酯可爲， 由聚酯樹脂，又以由聚對苯二甲酸乙二酯樹脂爲佳之成形 製品（纖維、薄膜、瓶等）再生之物。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -40· 581777 A7 B7 五、發明説明（38) (請先閲讀背面之注意事項再填寫本頁) 態樣（7 )之方法所得聚酯適用於製造纖維。該聚酯 之固有粘度（〇 —氯苯酚，35 °C )較佳爲0.40至0.80，更 佳爲0.45至0.75’特佳爲0.50至0.70。固有粘度低於 〇.4〇時，所得纖維強度將不足而不宜，又，固有粘度超 過0.8 0時，將所得聚酯供給熔融紡絲時，會過度提升聚 酯熔融物之粘度。 由態樣（7 )之聚酯樹脂形成聚酯纖維時，可採用態 樣（4 )所使用之方法。 實施例 下面將以實施例說明本發明。 又，對下列實施例及比較例所得之聚酯樹脂、纖維及 薄膜進行下列試驗。 1 .固有粘度： 於原氯苯酚50ml中，將聚酯〇.6g加熱溶解後，冷卻 至室溫，再利用奧氏式粘度管以3 5 °C之溫度條件測定， 經濟部智慈財產局員工消費合作社印製 其後由所得溶液粘度數據算出該聚酯之固有粘度（IV ) 〇 2 ·聚合物色調（顏色L値及顏色b値）： 2 90 °C，真空下，將聚合物試料熔融1〇分鐘後，於錦 板上將其成形爲原3.0 ± 1 .0mm板物後，馬上放入冰水中 急冷，再以160°C對板物進行1小時乾燥結晶化處理，其 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） • 41 - 581777 A7 _____B7_ 五、發明説明（39 ) (請先閲讀背面之注意事項再填寫本頁) 後將板物放置於色差計調整用白色標準板上，再利用蜜諾 塔公司製狩獵型色差計CR - 200測定供試板表面之顏色 L値及b値。其中，L値代表明亮度，數値愈大表示明亮 度愈局^ b値愈大表不黃色味程度愈筒。 3.含有金屬之濃度分析： 觸媒系中鈦原子濃度及磷原子濃度之分析法爲，於觸 媒溶液時，係直接塡入液體單之後又，含於聚酯樹脂中時 ，係於鋁板上先將粒狀聚酯樣品加熱熔融，再以壓縮板機 形成具有平面之成形物後，將各自樣品供給螢光X線裝 置（理學電機工業股份公司製3 270型）進行定量分析。 但，添加平光劑用氧化鈦之聚合物中，鈦原子濃度之 測定方法爲，將樣品溶解於六氟異丙醇中，以離心分離機 由該溶液使氧化鈦粒子沈源後，利用傾斜法回收上層澄淸 液，再將溶劑蒸發，而得測定用樣品。 4·二乙二醇（DEG )含量： 經濟部智慧財產局員工消費合作社印製 利用水合肼將聚合物分解後，利用氣相色譜儀（股份 公司日立製作所製「263 — 70」）測定分解生成物中二乙 二醇之含量。 5 ·延伸薄膜色調（顏色L値及顏色b値）： 將5枚雙軸延伸之聚酯薄膜重疊後，於乾燥機中以 1 60 °C將重合物熱處理90分鐘，結晶化後利用顏色機公司 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -42- 581777 A7 B7 五、發明説明（40) 製（M — 7 5 00型顏色和測定L値及b値。 (請先閱讀背面之注意事項再填寫本頁) 6.混濁度： 於乾燥機中以1 5 0 °C將粒狀聚合物樣品熱處理乾燥6 小時後，利用熔融擠押機以290 °C加熱熔融，再以回轉冷 卻筒擠押成片狀，急冷固化後，得厚500//m之未延伸薄 膜（片物）。由所得未延伸片選取數個表面無傷之部位作 爲樣品，再利用日本電色工業股份公司製混濁度計（HD Η —1 0 0 1 D Ρ )測定樣品之混濁度。 7 ·熱安定性（未延伸薄膜）： 求取混濁度測定用供試未延伸薄膜之固有粘度値（A )，及製作該未延伸薄膜用聚合物之固有粘度値（B)， 再由（B ) - （ A )之差値以下列基準判斷供試未延伸薄 膜之熱安定性。 特級……〇至〇·〇5 (熱安定性特優者） 一級......超過〇 · 〇 5至0 · 1 0 (熱安定性優良者） 二級......超過〇 · 1 〇至〇 · 1 5 (具熱安定性者） 經濟部智慧財產局員工消費合作社印製 三級......超過〇 · 1 5 (熱安定性差者） 8 ·熱安定性（雙軸延伸薄膜）： 將5枚雙軸延伸之聚酯薄膜重疊後，於乾燥機中以 1 6(TC將所得重合物熱處理90分鐘而結晶化；再求取所得 雙軸延伸薄膜之固有粘度値（A)，及製作該雙軸延伸薄 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -43- 581777 A7 B7 -—---------------- 五、發明説明（41 ) 膜用聚合物之固有粘度値（B) ’由（B) - （A)之差値 以下列基準判斷熱安定性。 特級：〇至0.05 (熱安定性特優者） (請先閲讀背面之注意事項再填寫本頁) ~級：超過〇 . 0 5至0 · 1 0 (熱安定性優良者） 二級：超過0 · 10至0.15 (熱安定性普通者） 三級：超過0 · 15 (熱安定性差） 9·分析對苯二甲酸二甲酯： (a) 2—羥基對苯二甲酸二甲酯量： 將對苯二甲酸二甲酯溶解於丙酮溶劑中，再利用氣相 色譜儀（裝置：休雷特公司製HP 5 890，毛細柱：J&amp;W公 司製DB — 17)及GC— MASS (裝置：休雷特公司製， GC/質量檢驗器=HP6890/HP5 9 73，毛細柱：J&amp;W公司製 DB — 1 7 )所得之質量分析，使溶液中2 -羥基對苯二甲酸 二甲酯之含量定量。 1 〇 .分析對苯二甲酸： 經濟部智慧財產局員工消費合作社印製 (a) 4—羥基苯甲醛、對甲苯酸、羥基苯甲醛之質量濃度 將供試對苯二甲酸樣品溶解於2N -氨水後，將溶液 供給島津製作所股份公司製液體色譜系統（LC 一 6A， STR 0 DS— Η柱），再由溶液分離出4 一羧基苯甲醛、 對甲苯酸及羥基苯甲醛，測定其質量濃度。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） Λ ^ -44 - 581777 A 7 B7 五、發明説明（42) (b)對苯二甲酸單甲酯之質量濃度： (請先閱讀背面之注意事項再填寫本頁) 將供試對苯二甲酸樣品供給高速液體色譜儀（裝置： 股份公司曰立製作所製HPLC D— 7000，塡充式柱：RP — 1 8 ; 2根），測定所含對苯二甲酸單甲酯之質量濃度。 (c )安息香酸質量濃度： 利用二偶氮甲烷將供試對苯二甲酸樣品酯化後，將該 酯供給以1 〇 % S E — 3 0爲分離柱之氣相色譜，再以η -十 三烷爲內部標準，測定安息香酸之質量濃度。 1 1 .紡絲噴嘴所產生之附著物層： 將供試聚酯成形爲片狀後，以290°C將其熔融，再由 孔徑0.15mm 0，孔數12個之紡絲噴嘴吐出，並以600 m/分之紡絲速度連續紡絲2天，以測定噴嘴吐出口外緣 所產生之附著物層的高度。該附著物層愈高時，表示吐出 之聚酯熔體的長絲狀流體易產生彎曲現象，而降低聚酯之 成形性。即，以紡絲噴嘴所產生之附著物層高度爲，聚酯 成形性之指標。 經濟部智慧財產局員工消費合作社印製 1 2 .纖維之拉伸強度、極限伸度： 依據JIS L 1013所記載之方法測定纖維的拉伸強度 及極限伸度。 [製造例1] 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -45- 581777 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（43 ) 合成偏苯三酸鈦之方法 將對偏苯三酸酐之莫耳比僅爲0.5的四丁氧基鈦加入 偏苯三酸酐2質量單位混合乙二醇98質量單位而得之乙 二醇溶液中，空氣，常壓下將混合物保持80°C，反應60 分鐘後冷卻至室溫，再以1 〇倍量之丙酮再結晶化，接著 以濾紙過濾析出物，以1 〇〇 °C乾燥2小時後，得目的鈦化 合物。 [實施例1 ] 於能加壓反應之SUS (不銹鋼）製容器中，將四一 n 一丁基鈦酸酯0.009質量單位混入對苯二甲酸二甲酯及乙 二醇7 0質量單位之混合物後，於0 . 〇 7 Μ P a加壓下由1 4 0 °C升溫至2 4 0 °C，以進行酯交換反應。其後將三乙基膦基 乙酸酯〇 · 〇 4質量單位加入反應混合物中，以結束酯交換 反應。 將反應生成物移入聚合容器後升溫至2 9 0 °C，再於 26.7Pa(0.2mmHg)以下之高真空下進行聚縮合反應，得 固有粘度0.60、二乙二醇含量1·5質量％ (對對苯二甲酸 乙二酯成分之莫耳量的比）之聚對苯二甲酸乙二酯樹脂。 由熔融紡絲裝置之吐出口連續將所得聚對苯二甲酸乙 二酯樹脂擠成單絲狀，冷卻後切斷，得約3 m m之粒狀顆 粒。以1 80°C將顆粒乾燥3小時後，將乾燥物供給熔融紡 絲步驟，以製作絲紗支數爲3 3 3 dtex/36fil之未延伸長絲 條，再將其延伸4.0倍，得絲紗支數爲8 3.2 5 dtex/36fil之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --··---=---裝------訂----- (請先閱讀背面之注意事項再填寫本頁) -46- 581777 A7 B7 五、發明説明（44 ) 延伸複型絲。 (請先閲讀背面之注意事項再填寫本頁) 又，將上述乾燥顆粒供給單軸混煉擠押機（內徑 6 5mm，徑路長l〇mm，滯留時間10分鐘）後，將擠押機 內溫度由2 8 0 °C緩升至3 0 0 °C以進行熔融混煉’再由模頭 將熔融聚酯擠出，得未延薄膜。以9 0 °C對未延伸薄膜進 行縱延伸倍率3.5倍，橫延伸倍率4.0倍之雙軸延伸後， 以200°C熱固定，得厚15//m之薄膜。 [實施例2] 同實施例1製造聚酯樹脂。但，使用鈦化合物用製造 例1所合成的偏苯三酸鈦0.016質量單位進行聚縮合反應 。所得聚酯組成物及使用其之纖維與未延伸薄膜的特性如 表1所示。 [實施例3至9及比較例1至7] 經濟部智慧財產局員工消費合作社印製 實施例3至9及比較例1至7各自同實施例1進行聚 縮合反應，得聚酯樹脂組成物。但，依表1所示變更鈦化 合物、磷化合物之種類及其添加量。所得聚酯樹脂及使用 其之未延伸薄膜的特性如表1所示。 [比較例8] 於可加壓反應之SUS製容器中，將四一 n 一丁基鈦酸 酯0.009質量單位混入對苯二甲酸二甲酯1〇〇質量單位及 乙二醇7 0質量單位之混合物中，0 · 0 7 Μ P a加壓下將混合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -47· 581777 A7 B7 五、發明説明（45 ) 物由140°C加熱升溫至240°C以進行酯交換反應，再加入 三乙基膦基乙酸酯〇·〇4質量單位’以結束酯交換反應。 (請先閱讀背面之注意事項再填寫本頁) 其後將三氧化銻〇 · 〇 5 3質量單位加入反應生成物中， 再移入聚合容器’升溫至 29〇°C後，於 26.67Pa( 0.2 mmHg)以下之高真空下進行聚縮合反應，得固有粘度 0.60、二乙二醇含量1.5質量％之聚酯樹脂。 [實施例10] 同實施例1製造聚酯樹脂後，由其製造纖維。但，將 鈦化合物及磷化合物變更爲表1所示化合物及添加量，結 束酯交換反應後，再加入平均粒徑〇.3//m之氧化鈦20質 量％及乙二醇漿液1 .5質量單位。測定結果如表1所示。 [實施例1 1 ] 經濟部智慧財產局員工消費合作社印製 同實施例1之方法製造聚酯樹脂及纖維。但，將鈦化 合物及磷化合物變更爲表1所示化合物及添加量，結束醋 交換反應後，再加入季戊四醇—四[3 -（3,5-二一 tert — 丁基—4一羥基苯基）丙酸酯（商標名：伊魯卡ι〇1〇，吉 巴斯公司製）0.02質量單位。測定結果如表1所示。Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives] Unreacted mixture of phosphorus compounds of at least one of the compounds shown in the above, the aforementioned reaction product (II) is the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -13- 581777 A7 ____ B7 V. Description of the invention (11) The reaction product of the aforementioned titanium compound component (1) and the aforementioned phosphorus compound component (2a), and the unreacted mixture (II) is the titanium compound component (1) and, (2 b) contains the following general formula (2) or (3): (R4) n- (〇) pP ~ (OH), II 0 (2) [In formula (2), R4 contains 2 to 18 carbons Atomic alkyl or aryl containing 6 to 20 carbon atoms; η is an integer of 1 or 2, and when η is 1, p is an integer of 0 or 1, and when η is 2, ρ is 0] 0 ( CH2 CH2 ~ 0)-,-a Η Η-(0-CH2 CH2) b ~ 0 卩 一 〇- (CH2CH2 —Ο Ο (3) (Please read the precautions on the back before filling this page) Wisdom of the Ministry of Economic Affairs Unreacted mixture of phosphorus compound components of at least one phosphorus compound as shown in formula (3), where m, ma, and mb are each independently an integer of 1 or 2 The content of titanium and phosphorus contained in the catalyst system used in the method of the present invention is adjusted to meet the requirements of the following formulae (a), (b), and (c). MTl $ 15 (a) 1 ^ (Mp / Mii) ^ 15 (b) 10 ^ (Mii + Mp) ^ 100 (c) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 581777 A7 B7 V. Description of the invention (12) In formulas (a), (b), and (c), MTi is the catalyst system (please read the precautions on the back before filling this page). Millimolar p-poly (aromatic dicarboxylic acid) containing titanium element The ratio of total moles of repeating units of aromatic dicarboxylic acid ethylene esters in ethylene glycol), Mp is the millimolar amount of phosphorus element in the catalyst system versus poly (aromatic ethylene glycol dicarboxylic acid) The ratio of total moles of repeating units of aromatic dicarboxylic acid ethylene ester in the ester). Also, in formula (a), MTi is corresponding to the titanium used in the transesterification reaction and the polycondensation reaction in the method of the present invention. The total amount of the compound component 成分. MTi 値 is preferably 2 or more and 15 or less, more preferably 3 or more and 10 or less, and particularly preferably 3 or more and 6 or less. When MTi 値 is less than 2, the target polyester resin is The yield will be insufficient, and the molecular weight of the obtained polyester will be less than expected. Also, when MTi is more than 15, the thermal stability of the obtained polyester resin will be insufficient, and when the polyester resin is processed at a high temperature, The molecular weight will be significantly lowered, and it will not be possible to obtain shaped articles with the required mechanical properties. The MT1 of the printed consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) is the same as the above, and Mp corresponds to the total amount of the phosphorus compound component (2a) or (2b) used in the transesterification reaction and the polycondensation reaction in the method of the present invention. That is, the Mp / MTi ratio 値 is preferably 1 or more and 15 or less, more preferably 2 or more and 15 or less, and particularly preferably 4 or more and 10 or less. When the Mp / MTi ratio is less than 1, the obtained polyester has a yellow taste, and when it exceeds 15, the obtained catalyst is used in the manufacture of polyester, and the polycondensation activity will be insufficient, making it difficult to obtain a polyester having a desired molecular weight. . That is, when Mp / MTi is 1 to 15, the polycondensation activity of the obtained catalyst system for the aromatic dicarboxylic acid ethylene glycol diester 'can be sufficiently increased to obtain a polyester resin having a desired molecular weight and good color tone. In the formula (c), the sum of MTi and Mp (MTi + Mp) is preferably 10 or more and 100 or less, and more preferably 20 or more and 70 or less. (MTi + Mp) is lower than the standard of this paper. Applicable to China National Standard (CNS) A4 specification (21 × 297 mm) -15- 581777 A7 B7 V. Description of invention (13) (Please read the notes on the back before filling (This page) At 10:00, the quality uniformity and forming processability of the obtained polyester resin will be insufficient. For example, when the obtained polyester resin is supplied to an electrostatic application method for film forming processing, the production yield will be insufficient. Due to the uneven thickness of the obtained film, sufficient film forming processability and impact resistance cannot be obtained. When (MTi + Mp) 値 exceeds 100, a foreign matter due to a catalyst system is generated in the obtained polyester resin, and transparency is insufficient. The aromatic dicarboxylic acid used in the method of the present invention is preferably terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 5-sulfoisophthalic acid metal salt, and 5-sulfoisophthalic acid. _ Selected in salt. The method of the present invention further comprises a step of producing an aromatic dicarboxylic acid and a glycol diester by using a diesterification reaction of the aromatic dicarboxylic acid and ethylene glycol. The diesterification reaction of the aromatic dicarboxylic acid and ethylene glycol can be in the absence of a catalyst or in the presence of a catalyst (such as an alkali metal salt, an alkaline earth metal salt), for example, from 0.05 to 0. It is carried out under a pressure of 20 MPa, or under reaction conditions such as a temperature of 230 to 280 ° C. Another aspect of the method of the present invention may further include the use of a lipid exchange reaction between a dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol to produce an aromatic dicarboxylic acid and a glycol diester. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Also, it can be in the presence of a catalyst at a temperature of 160 to 260 ° C and 0.05 to 0. A transesterification reaction of a dialkyl ester of an aromatic dicarboxylic acid and hexanediol was performed under a pressure of 20 MPa. During the transesterification reaction, the pressure is lower than 0. At 〇 5 MPa, the catalytic action of the titanium compound component (1) to promote the reaction will be insufficient, and more than 0. At 20MPa, a large amount of diethylene glycol is produced as a by-product, and the size of the obtained polymer paper conforms to the Chinese National Standard (CNS) A4 (210X297 mm) -16-581777 A7 B7 V. Description of the invention (14) Insufficient characteristics such as stability. (Please read the notes on the back before filling this page.) When the method of the present invention uses the two dibasic vinegars of aromatic diresidual acid, the base is preferably 1 to 5 carbon atoms, more preferably methyl, Ethyl or isopropyl. The dialkyl aromatic dicarboxylic acid used in the method of the present invention is preferably dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, diethyl terephthalate, It is selected from diethyl isophthalate and diethyl naphthalate. In the method of the present invention, the dialkyl ester of the aromatic carboxylic acid to be used for the transesterification reaction may be dimethyl terephthalate containing 80 mol% or more per mol. In addition, 70 mol% or more of the total amount of the aromatic dialkyl ester used for the transesterification reaction may be dialkyl terephthalate recovered after depolymerizing the polyalkylene terephthalate. However, the content of 2-hydroxyterephthalic acid in the dialkyl terephthalate recovered at this time is preferably controlled to less than 2 ppm. When printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the method of the present invention uses an ester exchange reaction of a dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol to produce an aromatic dicarboxylic acid and a glycol diester. When the transesterification reaction is carried out in the presence of a catalyst, the catalyst used for the transesterification reaction may be all or part of a polycondensation catalyst used in the method of the present invention. That is, the method of the present invention is performed in the presence of at least the above-mentioned catalyst, and does not react with the phosphorus compound component (2a) or (2b) or react with the phosphorus compound component (2a). After the transesterification reaction of dialkyl carboxylic acid and ethylene glycol, in the presence of paper containing at least the original paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable. -17- Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative 581777 A7 B7 --___ V. Description of the invention (15) The titanium compound component (1) after reaction or reaction, and the unreacted or reacted phosphorus compound component (2a) or unreacted phosphorus compound component ( 2b) Under a catalyst system, a reaction mixture containing an aromatic dicarboxylic acid and an ethylenediester obtained by a transesterification reaction is polycondensed to produce a poly (aromatic dicarboxylic acid &amp; diester) resin. In the method of the present invention, at least one selected from the group of titanium compound components (1 stomach) containing a titanium alkoxide, a titanium alkoxide and an aromatic polyvalent carboxylic acid or a dried reaction product group constituting a catalyst In the present invention, the titanium compound component (1) constituting the catalyst system is preferably too low to complete the oxide, preferably the following general formula (4): ίΤ6 Ί R5 -0- 一 Ti -0--R8 (4 ) ^ OR7 [wherein R5, R6, R7 and R8 are each independently selected from alkyl and phenyl groups containing 2 to 10 carbon atoms; me is an integer from 1 to 4] The titanium alkoxide is preferably, for example, titanium tetraisopropoxide, tetrapropoxy titanium, tetra-η-butoxy titanium, tetraethoxy titanium, tetraphenoxy titanium, octyl trititanic acid Salt, hexaalkyl dititanate, etc. In the present invention, the aromatic polyvalent carboxylic acid for the titanium compound component (1) constituting the catalyst system is preferably the following general formula (5): This paper scale is applicable to the country of China Standard (CNS) Α4 specification (210 × 297 mm) --- * ------- 0 ^ ------ 1T ------ ^ 9— Please read the notes on the back before filling in this (Page) • 18- 581777 A7 B7 5. Description of the invention (16) 〇T_H) na (5) [In the formula, na is an integer of 2 to 4] It is selected from the compounds shown. The aromatic polyvalent carboxylic acid or its anhydride is more preferably selected from among phthalic acid, trimellitic acid, pyromellitic acid and its anhydride. The reaction mode of the titanalkoxide and the aromatic polyvalent carboxylic acid (or its anhydride) is to mix the aromatic polyvalent carboxylic acid or its anhydride in a solvent and dissolve part or all of the titanane in the solvent, and then oxidize the titanane. The material is dropped into the mixed solution, and then heated at 0 ° C to 200 ° C for more than 30 minutes, and more preferably, 30 to 150 ° C for 40 to 90 minutes. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The solvent may be appropriately selected from those capable of dissolving part or all of the aromatic polyvalent carboxylic acid or its anhydride, but ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene, etc. are preferred. . There is no limitation on the molar ratio of the reaction of the titanalkoxide with the aromatic polyvalent carboxylic acid or its anhydride. However, when the titanium alkoxide ratio is too high, the color tone of the obtained polyester is deteriorated and the softening point is lowered. On the contrary, when the titanium alkoxide ratio is too low, the polycondensation reaction becomes difficult. Therefore, the molar reaction between the titanium alkoxide and the aromatic polyvalent carboxylic acid or its anhydride is preferably controlled to be 2/1 to 2/5. The reaction product obtained by this reaction can be directly supplied to the reaction with the phosphorus compound (2a), or it can be purified by recrystallization using a solvent formed from acetone, methanol, and / or ethyl acetate, and then reacted with the phosphorus compound component (2a). . One aspect of the catalyst system used in the method of the present invention is the use of titanium compounds. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page). Printed and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- 581777 A7 B7 V. Description of the invention (17) (Please read the precautions on the back before filling this page) Ingredients (1) and phosphorus compounds (2 a) Unreacted mixture or reaction product. The phosphorus compound component (20) contains at least one of the phosphorus compounds represented by the general formula (II). The phosphorus compound (phosphonate) represented by the general formula (1) is preferably methyl methyl methanephosphonic acid or methyl ester. Methylmethanephosphonic acid, propylmethylmethanephosphonic acid, butylmethylmethanephosphonic acid, methylmethyl-phosphono-phenylacetic acid, ethylmethyl-phosphono-phenylacetic acid, propylmethyl-phosphono-phenyl It is selected from dimethyl esters, diethyl esters, dipropyl esters, and dibutyl esters of acetic acid and butyl ester-phosphino-phenylacetic acid. Phosphorus compounds represented by general formula (1) (Phosphonate compound) The reaction to the titanium compound component (1) is slower, so the duration of the catalytic activity of the titanium compound in the polycondensation reaction can be lengthened, and the catalyst added by the polyester during the polycondensation reaction can be reduced. Addition amount. In addition, even if a large amount of stabilizer is added to the catalyst system of the phosphorus compound represented by the general formula (1), the thermal stability of the obtained polyester is not reduced, and the color tone is not deteriorated. Intellectual property of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperative Printed and Modified Titanium Compound Components (1) and Phosphorus Compound Components ( 2a) A method for reacting a product, mixing a phosphorus compound component (2a) composed of at least one phosphorus compound in formula (1) and a solvent, and dissolving part or all of the phosphorus compound component (2a) in the solvent, The titanium compound component (1) is dropped into the mixed solution, and the reaction system is generally heated at 50 ° C to 200 t: preferably 70 to 150 ° C for 1 minute to 4 hours, preferably 30 Minutes to 2 hours. The reaction pressure is not particularly limited and may be 10. 1 to 0. 5MPa), under normal pressure or reduced pressure (0. 001 to O. IMPa), and generally under normal pressure. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -20- 581777 A7 B7 V. Description of the invention (18) When the phosphorus compound component (2a) shown in the formula (1) for the above catalytic reaction is used The solvent used may be one that can dissolve at least part of the phosphorus compounds ((please read the precautions on the back before filling this page) 2 a), and there is no particular limitation, preferably, ethanol, ethylene glycol, trimethyl ether Diol, tetramethylene glycol, benzene, xylene, and the like are selected from at least one of the solvents formed, and in particular, the titanium compound component ( 1) The addition rate with the phosphorus compound component (2a) is set such that in the reaction product of the obtained titanium compound component (1) and the phosphorus compound component (2a) contained in the catalyst, titanium atom conversion of the titanium compound component (1) Molar amount (mTl) response to the phosphorus atom-converted molar amount (mp) of the phosphorus compound component (2a) The molar ratio mTi / mp is 1: 1 to 1: 3, preferably 1: 1 to 1: 2 . The Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives) The reaction product of the titanium compound component (1) and the phosphorus compound component (2a) is separated from the reaction system by centrifugal precipitation treatment or filtration, and can be directly used for manufacturing. Catalysts for polyesters, or recrystallized reaction products obtained by separation, for example, recrystallized from acetone, methanol, and / or water, and then refined using the obtained catalysts. There is no need to separate the reaction products from the reaction system. The reaction mixture containing the reaction product may be directly used as the catalyst-containing mixture. The catalyst used in the method of the present invention may be an unreacted mixture of the titanium compound component (1) and the phosphorus compound component (2a). The addition ratio of the titanium compound component (1) and the phosphorus compound component (2a) is preferably 'Molar amount equivalent to titanium atom of titanium compound component (η) (Molar amount equivalent to phosphorus atom of phosphorus compound component (2a) ( mp) ratio mTi / mp is -21-This paper size applies Chinese National Standard (CNS) A4 specification (210X297). 581777 A7 B7 _ V. Description of the invention (19) 1: 1 to 1:15, more It is 1: 2 to 1:10. (Please read the notes on the back before filling this page) Another aspect of the catalyst used in the method of the present invention is to mix the titanium compound component (1) with the general formula (2) ) And at least one phosphorus compound component (2 b) selected from the phosphorus compounds represented by general formula (3). Specific examples of the phosphorus compound represented by general formula (2) are when p is 0, such as phenylphosphonic acid, methyl Phosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthracenylphosphonic acid Acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-monocarboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5 -Dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxybenzene Phosphoric acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3,6 monotricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tris Carboxyphenylphosphonic acid, etc. Among them, monoarylphosphonic acid is preferred. Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by industrial and consumer cooperatives. Other specific examples of phosphorus compounds represented by general formula (2) are when P is 1, such as monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, and mono-η- Butyl phosphate, monohexyl phosphate, monogeneryl phosphate, monononyl phosphate, monodecyl phosphate, monolauryl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4- Lauryl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-mono (laurate) Phenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, monoanthryl phosphate, and the like. Specific examples of the phosphorus compound represented by the general formula (3), for example, tris (hydroxyethyl paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -22- 581777 A7 ___ B7 V. Description of the invention (2〇) oxygen Group) phosphate, tris (hydroxyethoxyethoxy) phosphate. (Please read the notes on the back before filling this page.) When the catalyst used in the method of the present invention is an unreacted mixture of the titanium compound component (1) and the phosphorus compound component (2b), the titanium compound component (1) The ratio rriTi / πΐρ of the titanium atom equivalent molar amount (mTi) to the neighboring atom equivalent molar amount (mp) of the phosphorus compound component (2b) is preferably 1: 1 to 1:15, more preferably 1: 2 to 1 ·· 1 0. Phosphorus compound components (2a) and (2b) containing phosphorus compounds represented by general formulae (1), (2), and (3) in a transesterification reaction of an aromatic dicarboxylic acid dialkyl ester and ethylene glycol, Even if it coexists with the titanium compound component (1) as a reaction product or an unreacted mixture, it has no adverse effect on the transesterification reaction, and in the polycondensation reaction of the aromatic dicarboxylic acid and the diester of ethylene glycol, and The titanium compound component (1) has strong catalyst activity. In the method for producing a polyester of the present invention, the polymerization starting material formed by the ethylene glycol diester (or its oligomer) of an aromatic dicarboxylic acid is polycondensed in the presence of a catalyst. The polycondensation reaction is preferably at 230 to 320 ° C under normal pressure or reduced pressure, and at 0. 05Pa to 0. 2 MPa is preferred, or under the above conditions, the polycondensation is 15 to 300 minutes. The catalyst used in printing the method of the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is composed of an unreacted mixture of a titanium compound component (1) and a phosphorus compound component (2a) or (2b). Before or at the beginning, the titanium compound component (1) is added to the reaction system in its entirety, and before or at the beginning of the polycondensation reaction, the phosphorus compound component (2a) or (2b) is added to the reaction system obtained by the transesterification reaction in its entirety. in. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 581777 A7 B7 V. Description of invention (21) (Please read the precautions on the back before filling this page) The catalyst is made of titanium When the reaction product of the compound component (1) and the phosphorus compound component (2a) is constituted, the reaction system can be added in its entirety before or at the beginning of the transesterification reaction, and after the transesterification reaction is completed, the reaction mixture is supplied to the polymer. Condensation reaction. In the method of the present invention, when an ethylene glycol diester of an aromatic dicarboxylic acid is prepared by using an ester exchange reaction, a part of the titanium compound component (1), a part of the titanium compound component (1), and a phosphorus compound component can be prepared before the ester exchange reaction The reaction product of (2a) or part of the phosphorus compound component (2a) is added to the reaction system, and the remainder is added to the reaction system during or at the end of the transesterification reaction and at least one stage before or during the polycondensation reaction. in. In the method of the present invention, when diethylene glycol is used to prepare an ethylene glycol diester of an aromatic dicarboxylic acid, all or part of the phosphorus compound component (2a) may be added to the diester before the diesterization reaction. In the esterification reaction system, the remainder is added to the reaction system during or at least one stage of the diesterification reaction and before or during the polycondensation reaction. Using the above method of the present invention, a poly (aromatic ethylene dicarboxylate) tree with good or no foreign matter formed by the catalyst system and having a good color tone can be obtained when printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polyester resin of the present invention can be added with a reaction stabilizer, for example, at which stage the polyester can be added when manufacturing polyester, and if necessary, more than one antioxidant, ultraviolet absorber, flame retardant, and fluorescent can be added. One or more of whitening agents, smoothing agents, colorants, defoamers and other additives. It is especially preferred that the polyester contains an antioxidant containing at least one hindered amine phenol compound. The content is preferably, for polyester quality of less than 1% by mass. This paper size applies Chinese National Standard (CNS) A4 specifications (210X297). ) -24- 581777 A 7 B7 5. Description of the invention (22) (Please read the precautions on the back before filling this page). When the content exceeds 1% by mass, the heat of the antioxidant itself deteriorates and the quality of the resulting product is deteriorated. The hindered amine phenol compound for antioxidants used in the polyester of the present invention may be pentaerythritol tetrakid [3-(3,5 -di-tert-butyl-4-hydroxyphenyl) propionate], 3,9- Bis {2— [3-(3 — tert —butyl-1, 4-meridyl-5—methylphenyl) propanyloxy] —1,1—dimethylethyl} -2,4,8, 10-tetraoxaspiro [5,5] i-alkane, 1,1,3-tris (2-methyl-1, 4-hydroxy-5, tert-butylphenyl) butane, 1,3,5 — Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy; yl) benzene, 1,3,5-tris (4-tert-butyl-3-hydroxyl -2,6-Dimethylbenzene) isophthalic acid, triethylene glycol, a bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-Hexanediol-bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-sulfur-diethylethyl-bis [3— (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl] [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. Selected. Also preferred are amine hindered phenol-based antioxidants and thioether-based secondary antioxidants. There is no particular limitation on the method for printing the amine hindered phenol antioxidants into polyesters by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and it is preferred to add it at any stage after the end of the transesterification reaction or the esterification reaction to the end of the polycondensation reaction. . In order to finely adjust the color tone of the obtained polyester, one of organic cyan pigments and inorganic cyan pigments, such as azo-based, triphenylmethane-based, quinoline-based, anthraquinone-based, and phthalocyanine-based, can be added in the polyester manufacturing stage. The color former formed above. Of course, the production method of the present invention does not require the use of an orthochromic agent containing an inorganic cyan pigment such as cobalt for reducing the melt heat stability of polyester. Therefore, in essence, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) • 25- 581777 A7 B7_____ V. Description of the invention (23) The polyester obtained by the method described does not contain cobalt. (Please read the precautions on the back before filling out this page) Among the polyesters obtained by the method of the present invention, the L 値 obtained by using a hunting-type color difference meter is generally 80. Above 0, b 値 is -2. 0 to 5. 0. When the L 値 of the polyester is less than 80 · 0, the whiteness of the obtained polyester is reduced, and a practically high whiteness molded article cannot be obtained. Also, b 値 is lower than -2. At 0, the yellow taste of the obtained polyester is reduced, but the green taste is increased. When b 値 exceeds 5.0, the yellow taste of the obtained polyester is enhanced, so it cannot be practically used for manufacturing a molded article. The L 値 of the polyester obtained by the method of the present invention is preferably 82 or more, particularly preferably 83 or more, and b 値 is preferably 1.0 to 4. 5, especially preferred is 0 · 0 to 0. 4. The L L and b 聚 of the polyacetate obtained by the method of the present invention were measured by the following methods. That is, the polyester sample was melted under vacuum at 290 ° C for 10 minutes, and then formed on an aluminum plate to obtain a thickness of 3. 0: h 1. A plate-shaped polyester test piece of 0 mm was placed in ice water and quenched, and then the plate-shaped test piece was dried at 160 ° C for 1 hour, and then subjected to crystallization treatment. Then the obtained plate-shaped test piece was placed for colorimeter adjustment The white standard plate is measured with, for example, CR-200, a vet wax type colorimeter manufactured by Minota Corporation, to measure the surface tone of a plate-shaped test piece on the standard plate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the inherent viscosity of the polyester of the present invention is not limited, and is preferably 0.5 to 1. 0. In this intrinsic viscosity range, melt-forming is easy 'and the strength of the obtained molded article can be improved. The intrinsic viscosity is more preferably from 0.50 to 0.5. 9, particularly preferred is from 0.05 to 0.8. The method for measuring the inherent viscosity of polyesters is ‘the test polyester is dissolved in orthochlorophenol and then measured at 35 ° C. As for the polyester obtained by solid-phase polycondensation, most of them are used in general bottles, etc. 26- This paper size applies to China National Standard (CNS) A4 specifications {210X 297 mm) 581777 A7 B7 V. Description of the invention (24) The inherent viscosity contained in the ester is between 0.7 and 0.0. 9(). In addition, the content of the cyclic trimer of the aromatic one residual acid and the ester of ethylene glycol is preferably 0. 5 wt% or less, and the acetaldehyde content is preferably 5 ppm or less. (Please read the precautions on the back before filling this page) The impure content of the poly (aromatic ethylene dicarboxylate) resin obtained by the method of the present invention, the content of chain element and germanium element is preferably controlled at 5 / 1000 mol% or less, more preferably 2/1000 millimolar%. When the content of antimony and germanium contained in the polyester exceeds 5/1 000 mol%, the resulting polyester will have a blackening phenomenon unique to antimony, and the germanium element will increase the manufacturing cost of the obtained polyester. Not appropriate. In order to control the content of antimony element and germanium element in poly (aromatic ethylene di-residue acid) resin to be less than 5/1 000 mol%, the supply of diesters of aromatic dicarboxylic acid and ethylene glycol for polycondensation can be controlled The content of antimony and germanium is achieved. Also, a polyester fiber can be produced from the poly (aromatic ethylene dicarboxylate) resin of the present invention. In this case, the 'poly (aromatic ethylene dicarboxylate) resin preferably contains polyethylene terephthalate as a main component. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and can be used to make polyester film from the poly (aromatic ethylene dicarboxylate) resin of the present invention. In this case, the poly (aromatic ethylene dicarboxylate) resin preferably contains polyethylene terephthalate as a main component. Further, a bottle-shaped polyester molded article can be produced from the poly (aromatic ethylene dicarboxylate) resin of the present invention. At this time, the poly (aromatic ethylene dicarboxylate) resin is preferably to apply the Chinese National Standard (CNS) A4 specification (210X 297 mm) to the paper size of the paper. -27- 581777 A7 B7 V. Description of the invention (25) Ethylene terephthalate is the main component. (Please read the precautions on the back before filling this page) The aspect (1) of the method of the present invention is that the polycondensation raw material used is preferably 80% by mass or more, and more preferably 85% by weight or more. Aromatic dicarboxylic acid ethylene glycol phthalate, and the content of antimony element and germanium element is limited to 5/1 000 mol% or less. The catalyst is used to meet the requirements (a), (B) and (c) to produce polyethylene terephthalate. In this aspect (1), an ethylene glycol aromatic dicarboxylic acid ester is produced by a transesterification reaction, and when 80 mol% or more of the alkyl group of the aromatic dicarboxylic acid is dimethyl terephthalate, Or all of the catalyst system used in the method of the present invention is added to the transesterification reaction system with a titanium compound component (1), at 0. 〇5 to 0. The transesterification reaction was performed under a pressure of 20 MPa, and the obtained aromatic dicarboxylic acid ethylene ester was supplied for polycondensation. The Intellectual Property Bureau of the Ministry of Economic Affairs (printed in this form (1) by the Industrial and Consumer Cooperatives), the obtained polyethylene terephthalate resin is 80% by weight or more, and preferably 85% by weight or more of polyethylene terephthalate. Ethylene formate resin, and other resins other than polyethylene terephthalate resin can be mixed. The polyethylene terephthalate resin refers to ethylene terephthalate as the main repeat unit Polyester. Also, the main repeating unit refers to 80 mol% or more, preferably 85 mol% or more of the total repeating unit, which is composed of ethylene terephthalate. Polyterephthalate When the ethylene formate resin is a copolymerized with a third component other than the ethylene terephthalate component, the third component (copolymerization component) such as 2,6-naphthalenedicarboxylic acid, isophthalic acid, Aromatic dicarboxylic acids other than terephthalic acid such as phthalic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 581777 A 7 B7 V. Description of the invention (26) (Please read the precautions on the back before filling this page) In this state (1), the inherent viscosity of the polyester resin (0-chlorophenol, 3 5 ° C) is preferably 0. 50 to 0. 80, more preferably from 0.55 to 0. 75, especially good for 0. 60 to 0. 70. When the aspect (1) polyethylene terephthalate resin is used for film forming, for example, in order to improve handleability, it may contain an average particle diameter of 0 · 0 5 to 5 · 0 &quot; m for inactivation. Particles 0 · 0 5 to 5 · 0% by weight. At this time, in order to maintain the characteristics of high transparency of the polyethylene terephthalate resin of the present invention, the smaller the particle size of the inactive particles added, the better, and the smaller the added amount, the better. Solvent-inactive particles such as colloidal silica, porous silica, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, oxide pins, kaolin, composite oxide particles, crosslinked polystyrene, propylene Based crosslinked particles, methacrylic based crosslinked particles, polysiloxane particles, and the like. In addition, when using ethylene terephthalate resin in various molded products such as films, fibers, and bottles, it may contain antioxidants, heat stabilizers, viscosity modifiers, plasticizers, hue improvers, nuclear agents, and ultraviolet rays as necessary. Various functional agents such as absorbents. The aspect (2) of the invention printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a catalyst system composed of an unreacted mixture or reaction product of a titanium compound component (1) and a phosphorus compound component (2a). The use of alkyl terephthalate, preferably dimethyl terephthalate, transesterification reaction with ethylene glycol (pressure: 0. 05 to 0. 20MPa) The terephthalic acid and ethylene glycol diester are prepared, and then polycondensed to produce polyethylene terephthalate resin. In this case, the composition of the catalyst system needs to be controlled so as to comply with the above requirements (a), (b), and (c). Polyester fibers were subsequently produced from this polyethylene terephthalate resin. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -29- 581777 Α7 Β7 V. Description of the invention (27) (Please read the precautions on the back before filling this page) The inherent viscosity of the polyester resin It is preferably 0. 40 to 0. 80, more preferably 0. 45 to 0. 75, especially good for 0. 50 to 0. 70. Inherent viscosity is less than 0. At 40 o'clock, the fiber strength will be insufficient and unfavorable, and more than 0. At 80, the inherent viscosity of the raw polymer will be excessive, which is inconsistent with economic benefits. In the aspect (2) of the method of the present invention, the method for manufacturing the polyester fiber is not particularly limited, and the currently known polyester melt spinning method can be used, and it is preferable to melt the polyester at 270 ° C to 300 ° C, for example. Thereafter, it is spun at a melt spinning speed of 400 to 5000 m / min. In this spinning speed range, sufficient fiber strength can be obtained, and stable winding can be achieved. In addition, the polyester fiber can be stretched after being wound up, or it can be stretched without the need to be continuously wound up and stretched. In order to give the polyester fiber of the present invention a soft touch, an alkali reduction treatment may be performed. When the polyester fiber is produced as described above, the shape of the spinning nozzle is not limited, and may be Η-shaped or non-Η-shaped 又 and 可 may be a knot for a hollow fiber. The aspect (3) of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is that the titanium compound component formed by the titanium compound oxide represented by the general formula (4) is present in a diol solvent, and the formula (1) Phosphorus compounds formed from phosphorous compounds are heated and reacted. Under the polycondensation catalyst system composed of the reaction products, for example, aromatics obtained by the esterification reaction of high-purity terephthalic acid and ethylene glycol. Group dicarboxylic acids, such as terephthalic acid and ethylene glycol diesters or oligomers thereof, are subjected to a polycondensation reaction to perform polycondensation to produce a poly (aromatic dicarboxylic acid ethylene glycol) resin. This poly (aromatic ethylene dicarboxylate) resin is then supplied to a film forming step to obtain a polyester film. In this aspect (3), the mole of the phosphorus atom to the titanium atom contained in the catalyst system used is preferably more than 1.0 and less than 8. 0, more preferably 2. Above 0 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X29 * 7mm) • 30- 581777 A7 B7___ 5. Description of invention (28) is less than 7. 0. (Please read the precautions on the back before filling in this page) When the unreacted titanium compound component (1) is mixed in the reaction product, 'the resulting polyester resin will be insufficient in color' and 'unreacted phosphorus is mixed in the reaction product In the case of the compound component (2a), the polycondensation reaction of ethylene glycol terephthalate is hindered. The reaction method of the titanium compound component (1) and the phosphorus compound component (2a) is a method of mixing the titanium compound component (1), the phosphorus compound component (2a), and a diol solvent, and then heating the mixture. The reaction product generally exists in a solution state. In order to carry out the reaction uniformly, a method of preparing a glycol solvent solution of the titanium compound component (1) and the phosphorus compound component (2a) separately and then mixing and heating is particularly preferred. In addition, when the reaction temperature is normal temperature, the reaction will be insufficient and the time required for the reaction will be too long. Therefore, in order to obtain the reaction product uniformly and efficiently, the reaction temperature is preferably 50 to 2001 :, and the reaction time is preferably 1 minute to 4 hours. The specific reaction temperature is, for example, when the diol used is ethylene glycol, preferably 100 ° C to 200 ° C, and the reaction time is more preferably 30 minutes to 2 hours. The catalyst used in this aspect (3) is preferably a polyester that conforms to the above requirements (a), (b), and (c). The printing industry manufactures the aspect (3) of the Intellectual Property Bureau of the Ministry of Economic Affairs ’s consumer cooperative. The method of the film may be that the poly (aromatic ethylene dicarboxylate) resin is melt-extruded and then quenched to obtain an unstretched film, and then the unstretched film is biaxially stretched. After the stretching treatment, if necessary, heat setting treatment and relaxation heat treatment may be performed. Aromatic dicarboxylic acids used, such as terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyethane. The paper standards are applicable to Chinese national standards. (CNS) A4 specification (210X297 mm) -31-581777 A7 B7 5. Description of the invention (29) or its ester-forming derivative. (Please read the notes on the back before filling this page.) The Fang Xiangyi residue acid can be used with a small amount of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Alicyclic di-residual acids, such as hexanedicarboxylic acid, may also be ester-forming derivatives. In addition, ethylene glycol can use a small amount (! Mol% or less) of trimethyl glycol, propylene glycol, tetramethyl glycol, neopentyl glycol, hexane methyl glycol, dodecyl glycol, cyclohexane dimethanol Isoalicyclic monoalcohols, aromatic diols such as bisphosphonium, argon, and 2,2-bis (4- 1 / 5-hydroxyethoxyphenyl) propane. Furthermore, it is possible to share polyfunctional compounds such as aromatic diresidual acids and small amounts (less than 1 mole%) of trimellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethan, pentaerythritol, and the like. The polyester used for the polyester film constituting the aspect (3) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is preferably terephthalic acid or its ester-forming derivative, p-aromatic dicarboxylic acid, 1000 mole%. The usage amount is 80 mol% or more, and preferably 90 mol% or more. The use amount of ethylene glycol or its ester-formable derivative to 100 mol% of aliphatic diol is 80 mol%. Above, polyethylene terephthalate is more preferably 90 mol% or more. In particular, more than 80 mol% of all dicarboxylic acid components used as raw materials are terephthalic acid. Polyethylene terephthalate obtained by esterification is preferred. Compared with polyethylene terephthalate using dimethyl terephthalate as raw material, polyethylene terephthalate using terephthalic acid as raw material does not require transesterification reaction catalyst, so no need to add transesterification Stabilizing agent for reaction catalyst inactivation. Therefore, it has the advantage that the interaction between the phosphorus compound and the titanium compound for the stabilizer can be suppressed, and the addition amount of the titanium compound can be reduced. A method for producing a polyester through an esterification reaction will be described in detail below. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) -32- 581777 A7 _ _B7 V. Description of the invention (30) (Esterification step) (Please read the precautions on the back before filling in this Page) In the production of polyester, an aromatic dicarboxylic acid and an aliphatic diol are first esterified. Specifically, a slurry containing an aromatic dicarboxylic acid and an aliphatic diol is prepared. In the slurry, the content of the aliphatic diol of 1 mole of aromatic dicarboxylic acid is generally 1. 1 to 1. 6 moles, preferably 1. 2 to 1. 4 moles. Thereafter, the slurry was continuously supplied to an esterification reaction step. It is better to carry out the esterification reaction in one stage during the self-recycling of the reactants, or when two or more esterification reaction groups are chained in series, and the distillation column is used under the condition that the aliphatic diol is refluxed. The water produced by the reaction was discharged out of the system. When the reactants are continuously esterified in one stage during the cycle, the reaction temperature is generally 240 to 280 ° C, and preferably 250 to 270 ° C. The reaction pressure is normal pressure to 0. The reaction is carried out under a reaction condition of 3 MPa. In general, the reaction is performed until the esterification rate is above 90%, and preferably above 95%. After the esterification step, an esterification reaction product (oligomer) of an aromatic dicarboxylic acid and an aliphatic diol can be obtained. The degree of polymerization of the oligomer is preferably 4 to 10. The obtained oligomer was thereafter supplied to the following polycondensation step. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (polycondensation step) The polycondensation catalyst is at a temperature above the melting point of polyester (generally 240 to 280 ° C) under the existence of the above polycondensation catalyst system and under reduced pressure. The oligomer obtained in the esterification step is polycondensed by heating. In the polycondensation reaction, the unreacted aliphatic diol and the aliphatic diol produced by the polycondensation are preferably distilled off. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 ° to 297 mm). -33- 581777 A7 B7 V. Description of the Invention (31) The reaction system is outside. (Please read the precautions on the back before filling this page) The polycondensation reaction can be performed in a single tank or divided into multiple tanks. For example, when the polycondensation reaction is carried out in two stages, the polycondensation reaction in the first tank is at a reaction temperature of 24 5 to 290 ° C, preferably 260 to 28 ° C, and a reaction pressure of 100 to lkPa, and 50 It is carried out under the optimal conditions of 2 kPa. The final polycondensation reaction in the second tank is at a reaction temperature of 265 to 300 ° C, and again at 270 to 290 1: better, the reaction pressure is 1000 to 10 Pa, and 500 to 30 Pa. Under best conditions. In this way, polyesters for constituting polyester films can be obtained. In general, the obtained polyesters are pellets (stripes) which are extruded in a molten state and then cooled. At this time, the limiting viscosity (hereinafter referred to as IV) of the obtained polyester is 0. 40 to 0. 80dl / g, preferably 0. 50 to 0. 70dl / g. The polyester film of the present invention may be a single-layered or double-layered laminated film. In addition, the laminated film may be a layer formed of the polyester film of the present invention in a single layer or more, but it is preferably a layer formed of the polyester film of the present invention in its entirety. Printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, and other manufacturing conditions such as extension conditions during film formation can be appropriately selected according to the physical properties of the target film, such as surface characteristics, density, and heat shrinkage. For example, at a temperature of [Tg — 10] to [Tg + 6 0] ° c (where Tg: glass transition temperature of polyester), the uniaxial direction (longitudinal or horizontal direction) of the unstretched film is extended by 2. 5 times or more, preferably 3 times or more, and then extending the direction perpendicular to the front extension direction to a temperature of Tg to [Tg + 30] ° C. More than 5 times, and preferably more than 3 times. If necessary, the longitudinal direction and / or the horizontal direction may be extended again. The area extension magnification obtained by multiplying the longitudinal extension magnification by the horizontal extension magnification is preferably 9 times or more, more preferably 12 to 35 times, and particularly good for this paper. The Chinese national standard (CNS) A4 specification (210X297) -34- 581777 A7 B7 V. Description of the invention (32) (Please read the precautions on the back before filling out this page) 15 to 30 times. After the extension treatment, heat fixation treatment may be performed, and if necessary, relaxation treatment may be performed before or after the heat fixation treatment. The temperature of the heat fixing treatment is preferably from [Tg + 70] to [Tm — 10]. (: (Wherein, Tm: melting point of polyester), for example, 180 to 250 ° C, and the heat fixing time is preferably 1 to 60 seconds. In order to improve the handling property, the polyester film of the present invention may be added with an average particle diameter of a lubricant 0 · 0 5 to 5 · 0 // m inactive particles 0 · 5 to 5. 0 weight 0 / 〇. The added inactive particles are colloidal silica, porous silica, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, aluminum oxide, chromium oxide, kaolin, composite oxide particles, crosslinked polystyrene, Acrylic-based crosslinked particles, methacrylic-based crosslinked particles, polysiloxane particles, and the like. In aspect (4) of the present invention, when a dialkyl ester of an aromatic dicarboxylic acid is subjected to a transesterification reaction with ethylene glycol in the presence of the above-mentioned catalyst system, and then polycondensed to produce a polyester resin, the aromatic A 70% by weight portion of the dialkyl esters of the group dicarboxylic acids is used, and the polyalkylene terephthalate is depolymerized and recovered as dimethyl terephthalate. The catalyst system at this time is preferably prepared so as to comply with the requirements (a), (b), and (c) described above. In the aspect (4) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the polyalkylene terephthalate used for depolymerization is preferably polyethylene terephthalate, particularly preferably, a recycled bottle Recycled polyester fiber products, recycled polyester film products, and polymer scraps produced during the manufacturing process of the products. When the dimethyl terephthalate obtained by depolymerizing the polyalkylene terephthalate is less than 70% by weight, the component contained in the finally obtained polyester or polyester fiber comes from the recovered p-benzene The proportion of dimethyl diformate will be reduced to 50%, which weakens the impression of environmentally flexible products. Terephthalic acid-35 obtained by depolymerizing polyalkylene terephthalate- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 581777 A7 _____B7 V. Description of the invention (33) Formic acid Dimethyl vinegar is preferably 80% by weight or more, more preferably 90% by weight or more. The method for depolymerizing polyalkylene terephthalate used in the present invention to produce dimethyl terephthalate is not The method is particularly limited, for example, a method of depolymerizing a polyalkylene terephthalate with ethylene glycol, transesterifying with methanol, and recrystallizing or distilling the obtained polydimethylparaformate for purification. The impure content in dimethyl terephthalate obtained from the depolymerization of polyalkylene terephthalate is preferably 2-hydroxyterephthalic acid. The polyester produced by the above method can be used. Used in the manufacture of fibers, films, bottles, etc. The method for producing the fiber may be the method described in the aspect (2), and the method for producing the film may be the method described in the aspect (3). Aspect (5) of the present invention is that a polyethylene terephthalate film is produced by the method of the present invention. At this time, the terephthalic acid (TA) used as the raw material is to control the content of impurities in the monomethyl terephthalate (MMT) content: 1000 ppm or less; 4-Carboxylbenzaldehyde (4-CBA), Total content of p-toluic acid (P-TA), benzoic acid (BA) and dimethyl terephthalate (HDT): 1 ppm or less. The terephthalic acid may be obtained by heating and depolymerizing the used polyester packaging material in an alkanediol, then performing a transesterification reaction treatment on the depolymerized product with methanol, and then obtaining the dimethyl terephthalate. (DMT) Water decomposed product. In addition, the polycondensation catalyst used is a reaction product of a titanium alkoxide represented by the general formula (4) and a phosphorus compound represented by the general formula (1), and the molar amount of phosphorus atoms contained in the catalyst is The molar ratio 値 of the titanium atom is preferably 1.  〇The above paper standards are in accordance with Chinese National Standards (CNS) A4 specifications (210 × 297 mm) ------ 1 ---- (Please read the notes on the back before filling this page), 11 Intellectual Property of the Ministry of Economic Affairs 笱Printed by Employee Consumer Cooperatives-36- Printed by Employee Consumption Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 581777 A7 B7____ V. Invention Description (34) is below 8. 0. In this aspect (5), in order to obtain terephthalic acid having an MMT content of 1,000 ppm or less, the hydrolysis reaction of DM T is preferably at a temperature of 2 30 to 260 ° C and a pressure of 3. 0 to 4. 7 ′ at 6 MPa (gauge pressure) is more preferably 250 to 260. (:, Pressure 4. 0 to 4. Process at 6 MPa (gauge pressure) for 2 to 3 hours. In addition, MeOH produced by the hydrolysis reaction can be removed by introducing steam for stripping into the reactor together with dimethyl ether as a by-product. The TA produced by the hydrolytic reaction is suspended or dissolved in water 'and discharged from the reactor. After that, it is subjected to a plurality of crystallization treatments and then collected by a solid-liquid separation method. The obtained TA cake is dried, pulverized, and slurried ', and then subjected to an esterification reaction and a polycondensation reaction. The MMT content of the terephthalic acid obtained by the above method is 1 000 ppm or less, and the total content of 4-CBA, p-TA, BA, and HDT is 1 ppm or less, so it is suitable as a polyester for films. When the MMT contained in TA is less than 1000 ppm, the diol terminal of polyethylene terephthalate obtained by the polycondensation reaction can be blocked to improve the thermal stability. When it exceeds 1 000 ppm, it will be reduced. Transparency of the obtained polyethylene terephthalate. In this aspect (5), the polyethylene terephthalate resin preferably has a TA component occupancy rate of 85 mol% or more based on the total acid component standard and a glycol component occupancy ratio based on the total diol component standard. It is 85 mol ° /. the above. Aspect (5) The polyethylene terephthalate polyester resin may contain poly (aromatic dicarboxylic acid alkyl diester) resins other than polyethylene terephthalate in a total amount of 15 mol% or less. , Where the acid component may be 2,6-naphthalene ---. --- r --- 9 ------ IT ------ φ— (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 (Mm) -37- 581777 A7 B7___ 5. Description of the invention (35) (Please read the notes on the back before filling out this page) Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid , 1,7-naphthalene dicarboxylic acid, isomers of other naphthalenedicarboxylic acids, isophthalic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, Aromatic dicarboxylic acids such as diphenyl ground dicarboxylic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid; aliphatics such as adipic acid, azelaic acid, and sebacic acid Dicarboxylic acid component; p-yS — selected from bifunctional carboxylic acid components such as oxyethoxybenzoic acid, 6-hydroxyhexanoic acid and other oxo acids, and diol components other than ethylene glycol may be used. Trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethyl glycol, neopentyl glycol, diethylene glycol, 1,1 monocyclohexanedimethanol, 1,4-methylenehexanedimethanol, 2,2 —Bis (4'-yS —hydroxyphenyl) propane, At least one selected from bis (4'-Θ-hydroxyethoxyphenyl), etc., and can be copolymerized with 10% or less of polyfunctional compounds. After the polyester resin obtained by the above method in the aspect (5) is melt-extruded and then rapidly cooled to obtain an unstretched film, the unstretched film is biaxially stretched to obtain a stretched poly film. After the stretching treatment, if necessary, the film may be subjected to heat-setting treatment and / or relaxation heat treatment. The aspect (6) of the present invention printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is that, in the presence of some of the above-mentioned catalyst systems, the used polyester materials are recovered through depolymerization, transesterification, and water decomposition treatment. Dimethyl phthalate, 70% by weight of aromatic dicarboxylic acid alkyl ester, and ethylene glycol were subjected to transesterification treatment, and the remaining part of the catalyst system was added to the next reaction system to make the transesterification reaction. Ester or its oligomer is polycondensed, and a polyester film is produced from the obtained polyester resin. The catalyst used at this time is a mixture of the titanium compound component (1) and the phosphorus compound component (2a), and the catalyst used in the transesterification reaction is the titanium compound component (this paper size applies to the Chinese National Standard (CNS ) A4 specification (210X297 mm) -38- 581777 A7 B7 V. Description of the invention (36) (Please read the notes on the back before filling out this page) 1), add it when the polycondensation reaction of the obtained ester or oligomer Phosphorus compound component (2a). The catalyst system preferably meets the requirements (a), (b), and (c) described above. The content of the ethylene terephthalate repeating unit in the obtained polyester resin is preferably 80 mol% or more with respect to the total amount of the repeating unit. The dicarboxylic acid component and the diol component of the non-terephthalate repeating unit in the polyester resin may be those described in the aspect (5). In the manufacturing method of the aspect (6), when the dimethyl terephthalate obtained by depolymerizing the polyalkylene terephthalate is used as the dialkyl ester of the aromatic dicarboxylic acid in the polyester raw material, The content is preferably 50 mol of the total acid component for polyester. /. the above. The polyalkylene terephthalate is preferably polyethylene terephthalate. Particularly preferred are recycled PET bottles, recycled polyester fiber products, recycled polyester film products, and the production process of the product. Polyester scrap and other recycled polyester. Printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the content of dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate is less than 70% by mass, the resulting polyester or The ratio of the components derived from dimethyl terephthalate in the components contained in the ester film was reduced to 50%, and the reuse efficiency of the used polyester products was insufficient. In addition, the content of the dimethyl terephthalate obtained by depolymerizing the polyalkylene terephthalate to the total amount of the total dialkyl aromatic dicarboxylic acid is preferably 80% by weight or more, more preferably 90% by weight or more. When using regenerated dimethyl terephthalate, its production method is not particularly limited. For example, it can be depolymerized with ethylene glycol and then transesterified with methanol. The size of the obtained dimethyl terephthalate paper is in accordance with Chinese National Standard (CNS) A4 (21 × 297 mm) -39 · 581777 A7 B7 V. Description of the invention (37) (Please read the precautions on the back before (Fill in this page) Refining by crystallization or distillation. In the dimethyl terephthalate obtained by depolymerizing the polyterephthalate, the 2-hydroxyterephthalic acid content of the impurities is preferably 2 ppm or less. The inherent viscosity of the polyester used in the polyester film is preferably 0. 50 to 0. 80 is more preferably 0.55 to 0. 75, especially good for 0. 60 to 0. 70. When the intrinsic viscosity is within this range, sufficient film strength can be obtained without excessively increasing the intrinsic viscosity of the raw material polymer, which is economical. In addition, the method for producing the polyester film is not particularly limited, and the polyester resin can be melt-extruded and then rapidly cooled to obtain an unstretched film, and then the unstretched film is biaxially stretched. After the stretching treatment, if necessary, heat setting treatment and / or relaxation heat treatment may be performed. In aspect (7) of the present invention, when a polyester resin having ethylene terephthalate structure as the main repeating unit is manufactured, the catalyst system used is titanium compound component (1) and general formula (2) ) Or (3) is a mixture of a phosphorus compound component (2b) formed by at least one of the phosphorus compounds, and the titanium alkoxide used in the titanium compound component (1) is preferably a compound represented by general formula (4) Selected. The catalyst used in this aspect (7) preferably conforms to the above requirements (a), (b), and (c). In the aspect (7) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the ethylene glycol terephthalate or its oligomer is preferably an ester of dialkyl terephthalate and ethylene glycol. It is obtained by an exchange reaction, and the dialkyl terephthalate is preferably dimethyl terephthalate. Some or all of the dimethyl terephthalate to be used in the transesterification reaction may be recycled from polyester resin and also formed products (fiber, film, bottle, etc.) preferably made of polyethylene terephthalate resin. Thing. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -40 · 581777 A7 B7 V. Description of the invention (38) (Please read the precautions on the back before filling this page) Method of form (7) The resulting polyester is suitable for making fibers. The inherent viscosity of the polyester (0-chlorophenol, 35 ° C) is preferably 0. 40 to 0. 80, more preferably 0. 45 to 0. 75 ’special is 0. 50 to 0. 70. Inherent viscosity is less than 0. At 40, the strength of the obtained fiber will be insufficient and unfavorable, and the inherent viscosity will exceed 0. At 80, when the obtained polyester is supplied to melt spinning, the viscosity of the polyester melt is excessively increased. When the polyester fiber is formed from the polyester resin in the aspect (7), the method used in the aspect (4) can be adopted. Examples The present invention will be described below by way of examples. The polyester resins, fibers, and films obtained in the following examples and comparative examples were subjected to the following tests. 1 . Intrinsic viscosity: In 50 ml of orthochlorophenol, the polyester was 0.1. After 6g is dissolved by heating, it is cooled to room temperature, and then measured at 35 ° C using an austenitic viscosity tube. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the polyester viscosity is calculated from the obtained solution viscosity data. Intrinsic viscosity (IV) 〇2 · Polymer hue (color L 値 and color b 値): 2 90 ° C, the polymer sample was melted under vacuum for 10 minutes, and then formed into the original 3. 0 ± 1. Immediately after 0mm board, put it in ice water to quench it, and then dry and crystallize the board at 160 ° C for 1 hour. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) • 41-581777 A7 _____B7_ V. Description of the invention (39) (Please read the precautions on the back before filling this page) Place the board on the white standard board for colorimeter adjustment, and then use the hunting colorimeter CR made by Minota Corporation- 200 Determine the color L 値 and b 値 of the surface of the test plate. Among them, L 値 stands for brightness, and the larger the number 表示, the brighter the brightness is. 3. Analysis of metal-containing concentration: The analysis method for the concentration of titanium atom and phosphorus atom in the catalyst system is: in the catalyst solution, after it is directly inserted into the liquid sheet, and when it is contained in the polyester resin, it is firstly on the aluminum plate. Granular polyester samples were heated and melted, and then formed into flat shaped articles by a compression plate machine, and the respective samples were supplied to a fluorescent X-ray apparatus (Ricoh Electric Industrial Co., Ltd. Model 3 270) for quantitative analysis. However, in a polymer containing titanium oxide for a flattening agent, the titanium atom concentration is measured by dissolving a sample in hexafluoroisopropanol, sinking the titanium oxide particles from the solution with a centrifugal separator, and then using the tilt method The upper clear solution was recovered, and the solvent was evaporated to obtain a sample for measurement. 4. Diethylene glycol (DEG) content: Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, using hydrazine hydrate to decompose the polymer, and then measuring the decomposition generation using a gas chromatograph ("263 — 70" manufactured by Hitachi, Ltd.) Diethylene glycol content. 5 · Hale of stretched film (color L 値 and color b 値): After superimposing 5 biaxially stretched polyester films, heat-treat the remix in a dryer at 1 60 ° C for 90 minutes. Use a color machine after crystallization The paper size of the company applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -42- 581777 A7 B7 V. Description of the invention (40) (M-7500 type color and measurement of L 値 and b 値. (Please (Read the notes on the back before filling out this page) 6. Turbidity: After drying the granulated polymer sample in a dryer at 150 ° C for 6 hours, it is heated and melted at 290 ° C by a melt extruder, and then extruded into a sheet by a rotary cooling drum, and quenched and solidified. Then, an unstretched film (sheet) having a thickness of 500 // m was obtained. From the obtained unstretched sheet, several non-injured parts were selected as samples, and the turbidity of the sample was measured using a turbidimeter (HD Η 10,000 DP) manufactured by Nippon Denshoku Industries Co., Ltd. 7 · Thermal stability (unstretched film): Calculate the intrinsic viscosity 値 (A) of the unstretched film for turbidity measurement, and the intrinsic viscosity 値 (B) of the polymer used to make the unstretched film. B)-(A) The difference between the following criteria is used to judge the thermal stability of the unstretched film to be tested. Special grade ... 〇 ～ 〇05 (the person with excellent thermal stability) Grade one. . . . . . Above 〇 · 〇 5 to 0 · 10 (those with excellent thermal stability) . . . . . More than 0 · 10 to 0 · 15 (for those with thermal stability) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Level 3. . . . . . Exceeding 0. 15 (those with poor thermal stability) 8 · Thermal stability (biaxially stretched film): After superimposing 5 biaxially stretched polyester films, heat-treat the obtained heavy compound at 16 (TC) in a dryer Crystallize in 90 minutes; then find the intrinsic viscosity 値 (A) of the obtained biaxially stretched film, and make the biaxially stretched thin paper. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -43- 581777 A7 B7 ---------------------- 5. Description of the invention (41) Intrinsic viscosity of polymer for film 値 (B) 'from (B)-(A) difference 値The thermal stability was judged on the following basis. Special grade: 0 to 0. 05 (excellent thermal stability) (Please read the notes on the back before filling this page) ~ Level: more than 〇.  0 5 to 0 · 1 0 (excellent thermal stability) Level 2: More than 0 · 10 to 0. 15 (ordinary thermal stability) Level 3: Over 0 · 15 (poor thermal stability) 9 · Analysis of dimethyl terephthalate: (a) Amount of 2-hydroxy dimethyl terephthalate: Dimethyl formate was dissolved in an acetone solvent, and a gas chromatograph (apparatus: HP 5 890, manufactured by Hullet, capillary column: DB — 17 manufactured by J &amp; W), and GC-MASS (apparatus: Hullet, Made by the company, GC / mass tester = HP6890 / HP5 9 73, capillary column: J &amp; W company DB—17) Mass analysis obtained to quantify the content of dimethyl 2-hydroxyterephthalate in the solution. 1 〇. Analysis of terephthalic acid: printed by (a) 4-hydroxybenzaldehyde, p-toluic acid, and hydroxybenzaldehyde in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. After dissolving the test terephthalic acid sample in 2N-ammonia water, The solution was supplied to Shimadzu Corporation's liquid chromatography system (LC-6A, STR 0 DS-Pillar column), and 4-monocarboxybenzaldehyde, p-toluic acid and hydroxybenzaldehyde were separated from the solution, and their mass concentrations were measured. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Λ ^ -44-581777 A 7 B7 V. Description of the invention (42) (b) Mass concentration of monomethyl terephthalate: (please first Read the notes on the back and fill in this page) Supply the test terephthalic acid sample to the high-speed liquid chromatograph (apparatus: HPLC D-7000 manufactured by Yueli Manufacturing Co., Ltd., packed column: RP — 1 8; 2) , Determine the mass concentration of monomethyl terephthalate. (c) Mass concentration of benzoic acid: After the test terephthalic acid sample is esterified with diazomethane, the ester is supplied to a gas chromatograph with a separation column of 10% SE-30, and then η-ten Trioxane is an internal standard for determining the mass concentration of benzoic acid. 1 1. Adhesive layer produced by the spinning nozzle: After the test polyester is formed into a sheet, it is melted at 290 ° C, and then the hole diameter is 0. The spinning nozzle with a diameter of 15 mm 0 and 12 holes was ejected, and continuously spun at a spinning speed of 600 m / min for 2 days to measure the height of the adherent layer generated at the outer edge of the nozzle ejection opening. The higher the adherence layer, the filament-like fluid indicating the discharged polyester melt is prone to warp, and the moldability of the polyester is lowered. That is, the height of the adherent layer generated by the spinning nozzle is an index of the moldability of the polyester. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2. Tensile strength and ultimate elongation of the fiber: The tensile strength and ultimate elongation of the fiber were measured according to the method described in JIS L 1013. [Manufacturing example 1] This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -45- 581777 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (43) Synthetic trimellitic acid The titanium method has a molar ratio of trimellitic anhydride of only 0. Add 5 tetrabutoxytitanium to trimellitic anhydride 2 mass units mixed with 98 mass units of ethylene glycol. In the ethylene glycol solution obtained by mixing 98 mass units of ethylene glycol, air, keep the mixture at 80 ° C under normal pressure, cool to room temperature after 60 minutes, The crystal was recrystallized with a 100-fold amount of acetone, and then the precipitate was filtered through filter paper and dried at 1000 ° C. for 2 hours to obtain the target titanium compound. [Example 1] In a SUS (stainless steel) container capable of pressure reaction, tetra-n-butyl titanate 0. 009 mass units are mixed with a mixture of 70 mass units of dimethyl terephthalate and ethylene glycol.  〇 7 MPa Under pressure, the temperature was raised from 140 ° C to 240 ° C to carry out the transesterification reaction. Thereafter, triethylphosphinoacetate 4.0 mass unit was added to the reaction mixture to end the transesterification reaction. The reaction product was transferred to a polymerization vessel and heated to 290 ° C, and then at 26. 7Pa (0. 2mmHg) The polycondensation reaction is performed under a high vacuum to obtain an inherent viscosity of 0. 60. A polyethylene terephthalate resin having a diethylene glycol content of 1.5% by mass (a molar ratio of ethylene terephthalate component). The obtained polyethylene terephthalate resin was continuously extruded into a monofilament shape from the discharge port of the melt-spinning device, and was cooled and cut to obtain granular particles of about 3 mm. After drying the granules at 1 80 ° C for 3 hours, the dried material was supplied to the melt spinning step to produce unstretched filaments with a yarn count of 3 3 3 dtex / 36fil, and then stretched 4. 0 times, the number of silk yarns is 8 3. 2 5 dtex / 36fil This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- = --- install ------ order ----- (please first Read the notes on the back and fill out this page) -46- 581777 A7 B7 V. Description of the invention (44) Extending the polyfilament yarn. (Please read the precautions on the back before filling in this page.) After supplying the above-mentioned dry pellets to a uniaxial kneading extruder (inner diameter 65 mm, path length 10 mm, residence time 10 minutes), it will be squeezed The temperature inside the machine is gradually increased from 280 ° C to 300 ° C for melt-kneading, and then the molten polyester is extruded from the die to obtain an unstretched film. Longitudinal stretch ratio of unstretched film at 90 ° C 3. 5 times, horizontal extension ratio 4. After biaxial extension of 0 times, it was heat-fixed at 200 ° C to obtain a 15 // m thick film. [Example 2] A polyester resin was produced in the same manner as in Example 1. However, the titanium compound was synthesized using Production Example 1 titanium trimellitate 0. 016 mass units for polycondensation reactions. Table 1 shows the properties of the obtained polyester composition and the fibers and unstretched films using the same. [Examples 3 to 9 and Comparative Examples 1 to 7] Examples 3 to 9 and Comparative Examples 1 to 7 were printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the polycondensation reaction was performed with Example 1 to obtain polyester resin compositions . However, the types of titanium compounds and phosphorus compounds and their addition amounts were changed as shown in Table 1. The properties of the obtained polyester resin and the unstretched film using the same are shown in Table 1. [Comparative Example 8] In a SUS-made container capable of pressure reaction, tetra-n-butyl titanate 0. 009 mass units are mixed into a mixture of 100 mass units of dimethyl terephthalate and 70 mass units of ethylene glycol. Under the pressure of 0.07 MPa, the paper will be sized according to the Chinese National Standard (CNS). A4 specification (210X297 mm) -47 · 581777 A7 B7 V. Description of the invention (45) The product was heated from 140 ° C to 240 ° C for transesterification reaction, and then triethylphosphinoacetate was added. 4 mass units' to end the transesterification reaction. (Please read the precautions on the back before filling this page.) Then add antimony trioxide 〇. 05 3 mass units to the reaction product, and then transfer it to the polymerization vessel ’after heating to 29 ° C, at 26. 67Pa (0. 2 mmHg) The polycondensation reaction is carried out under a high vacuum to obtain an inherent viscosity of 0. 60.Diethylene glycol content 1. 5 mass% polyester resin. [Example 10] After the polyester resin was produced in the same manner as in Example 1, fibers were produced therefrom. However, the titanium compound and the phosphorus compound were changed to the compounds and addition amounts shown in Table 1, and after the transesterification reaction was completed, the average particle diameter was added. 3 // m of titanium oxide 20 mass% and ethylene glycol slurry 1. 5 mass units. The measurement results are shown in Table 1. [Example 1 1] Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The same method as in Example 1 was used to produce polyester resin and fiber. However, the titanium compound and phosphorus compound were changed to the compounds and addition amounts shown in Table 1. After the vinegar exchange reaction was completed, pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) was added. ) Propionate (brand name: Iluka 010, manufactured by Gibbs Corporation) 0. 02 mass units. The measurement results are shown in Table 1.

[實施例12J 將對苯二甲酸200質量單位及乙二醇105質量單位之 混合漿液放入備有攪拌機、精餾塔及水餾出冷凝器之反應 器中’ 270它、0.3 MPa加壓下進行240分鐘酯化反應。去 -48- 本氏張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 B7 五、發明説明（46 ) 除一半所得反應物後，將殘留一半保持2 5 0 °C，常壓下再 以150分鐘將對苯二甲酸1〇〇質量單位及乙二醇漿液52 質量單位供給反應系，其後於常壓下進行9 0分鐘酯化反 應。其間將反應系內溫度保持於2 5 0 X：。 又，去除一半所得反應物後，同樣地供應對苯二甲酸 1〇〇質量單位及乙二醇漿液52質量單位，以進行酯化反 應，接著重覆該步驟直到反應物中二乙二醇量安定。 反應物中二乙二醇量安定後，將一半酯化反應所得反 應物移入聚縮合反應裝置中，再加入預備用實施例1所得 之欽觸媒0.018質量單位及三乙基膦基乙酸酯0.040質量 單位，升溫至285 °C後，於26.67Pa以下之高真空下進行 聚縮合反應，得固有粘度〇 · 6 2、二乙二醇量1 · 〇質量％之 聚酯，再同實施例1製造纖維。測定結果如表1所示。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -49- 581777 A7 B7 五、發明説明（47 經濟部智慈財產局員工消費合作社印製 1« 截維特性 噴嘴面 異物高 度(㈣ m 寸 寸 CN 对 cn 寸 cn m on CN 对 对 m 極限伸 度(％) Οί rs OO CNJ CN IT) CN 03 On CN R OO 03 s 03 CN a OC CNJ f | oq rn OO VO cn OC … OC cn OC cn S OJ CO 二 \〇 ON 未延伸薄膜特性 s § s o s 〇 g O o' CNJ p 〇 s o s 〇 g o 無法製膜 i 無法製膜 g o I 無法製膜 § 混濁値 CN o CN CN CsJ CN rn cn 03 cn ON — Γ 聚酯聚合物 色調 s oo οά CO o5 m cn rn p VO v〇 S cn 〇 S § p ρ S oi o gN p § 〇 oc o g 〇 OO ο 〇 〇 OO to 卜 oo p o o cn oo o rn oo o oc ο O o &gt; ：0.620 | 0.620 1 | 0.620 | 0.620 Γ 0.600 1 | 0.600 1 0.600 0.600 0.600 [0.620 I 0.620 I 0.620 1 0.640 1 0.640 I 0.450 0.520 1 0.600 I 1 0.600 1 | 0.640 ] • 1 • • 1 • • 1 8 04 1 • 1 • 1 • • 与_ • 1 1 秦 1 1 • 1 • cn • 1 • 1 1 • 1 • Sb化合 物 (Sb£)3)毫 莫耳％ • ' 1 1 1 1 1 • • 1 • • 1 • • • Μϋ+Μρ 1 m m wn m IT) m oc in m m vn m m m VO m s VO un On s ON CO Μγ/Μτι 莫耳 vo v〇 v〇 v〇 卜 VO VO cn r- vd OO —· υη rn VO 1磷化合物| 含量 (毫莫耳 %) 沄 jo O 8 卜 種類 ΤΕΡΑ ΤΕΡΑ ω ω CL· ω 3： ΤΕΡΑ ΤΕΡΑ 正磷酸 TMP ΤΕΡΑ I ΤΕΡΑ I ΤΕΡΑ I ΤΕΡΑ 1 ΤΕΡΑ I ΤΕΡΑ 1 ΤΕΡΑ I ΤΕΡΑ I [ΤΕΡΑ I 1 ΤΕΡΑ 1 ΤΕΡΑ &lt;π Λ3 含量 (毫莫耳 %) m m VO m as oa on 種類 TBT TMT TMT TMT TMT TMT TMT TMT I 氧化 鈦 TMT TMT TMT TMT TMT TMT TMT TMT TMT TBT 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例H 實施例12 比較例1 比較例2 比較例3 比較例5 比較例6 比較例7 比較例8 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -50- 581777 A7 B7 ______一 五、發明説明（48 ) [製造例2](合成觸媒） π请先聞讀背面之注意事項存填寫本頁) 將乙二醇808g及乙酸50g放入備有能混合攪拌溶液 之機能的2 Z三口烷瓶中混合攪拌，再緩緩加入鈦四丁氧 化物1 4 2 g ’得鈦化合物之透明乙二醇溶液。將該溶液稱 爲「T B溶液」。利用螢光X線測得之T B溶液的鈦濃度 爲 2 · 0 %。 又，將乙二醇放入備有能加熱及混合攪拌之機能的2 《三口燒瓶中，攪拌下加入三乙基膦基乙酸酯2 2 4 g，得 透明溶液，並將該溶液稱爲「TP 1溶液」。 其次，將TP 1溶液加熱控制於1 6 0 °C，攪拌下將預先 準備之TB溶液400g緩緩加入TP1溶液中，加入全量後 6 0 °C下持續攪拌1小時，以結束鈦化合物成分與磷化合物 成分之反應。此時，將TP 1溶液及TB溶液之添加比調整 爲，對酞原子之磷原子莫耳濃度比爲6.0。所得反應生成 物可溶於乙二醇，且帶淡黃色味之溶液。將該溶液稱爲「 TT—觸媒」。 [製造例3] 經濟部智慧財產局g(工消費合作社印製 同製造例2之裝置及順序進行反應，得觸媒。但，如 下列所示變更製造例2所記載之TP 1溶液的調整量及添 加量。基本上將乙二醇1 045 g放入同上述之反應器中，攪 拌下加入三乙基膦基乙酸酯7 5 g，得透明溶液。將該溶液 稱爲「TP2溶液」。其次，將TP2溶液加熱控制於120°C ，攪拌下緩緩加入預備之TB溶液400g，加入全量後120 -51 - 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） 581777 B7 五、發明説明（49 ) (請先閱讀背面之注意事項再填寫本頁) °C下持續攪拌3小時’以結束鈦化合物與磷化合物之反應 。此時將TP2溶液與TB溶液之添加比調整爲，對鈦原子 之隣原子旲耳t辰度比爲2.0，得透明溶液。將該溶液稱爲 「TT一 2溶液」。 [實施例1 3 ] 對預先滯留對苯二甲酸乙二醇酯之低聚物的反應器進 行攪拌的同時，於氮氣中維持2 5 5 °C，常壓之條件下，以 均一供給速度供給高純度對苯二甲酸1 7 9單位及乙二醇 9 5單位混合而得之漿液，並將反應所產生之水及乙二醇 餾去系外，持續4小時酯化反應後結束反應。此時酯化率 爲9 8%以上，所生成之低聚物聚合度約爲5至7。 將酯化反應所得之低聚物225單位移入聚縮合反應槽 ，再混合聚縮合觸媒用製造例2所記載之鈦-磷反應化合 物TT — 6觸媒溶液0.182單位。其後各自階段性將系內反 應溫度由2 5 5 °C升至29(TC，及將反應壓力由大氣壓減至 6 OPa後，將反應所產生之水及乙二醇去除系外，同時進 行聚縮合反應。 經濟部智慧財產局員工消費合作社印製 監控系內攪拌翼負荷的同時，檢驗聚縮合反應之進度 ，當達所希望之聚合度時，結束反應。此時之聚縮合反應 時間爲1 60分鐘。其後由熔融紡絲裝置之吐出口連續將系 內反應物擠押成單絲狀，冷卻後切斷，得約3mm粒狀顆 粒。以1 80 °C將該顆粒乾燥3小時後供給單軸混煉擠押機 (內徑65mm、徑路長1 000mm、滯留時間10分鐘），將 -52- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 B7 五、發明説明（50) (請先閱讀背面之注意事項再填寫本頁) 擠押機內溫度由2 80 °C緩升至3 00°C以進行熔融混煉後， 由模頭擠出熔融聚酯，得未延伸薄膜。以90 °C對未延伸 薄膜進行縱延伸倍率3 · 5倍、橫延伸倍率4 · 0倍之雙軸延 伸，再以200°C熱固定，得厚15μηι薄膜。 [實施例Μ] 同實施例13進行聚縮合反應及製膜。但，將聚縮合 觸媒變更爲製造例3所得之鈦-磷反應化合物ΤΤ - 2溶 液。此時之聚縮合反應時間爲1 3 5分鐘。 所得聚酯粒狀顆粒及聚酯薄膜之特性如表2所示。 [實施例15] 同實施例13進行聚縮合反應，得聚酯薄膜。但，將 對目的聚合物量爲〇.3ppm之調色劑用氯唑藍（簡稱Β劑 )加入製造例2所得的鈦一磷反應化合物溶液T T - 6中 。此時令聚縮合反應時間爲1 60分鐘。 所得聚酯粒狀顆粒及聚酯薄膜之特性如表2所示。 經濟部智慧財產局員工消費合作社印製 [實施例16] 同實施例1 3進行聚縮合反應及製膜。但，以製造例 2所得之TB溶液及TP1溶液於不反應下，分別投入TB 溶液0.129單位、TP1溶液0.3 72單位作爲觸媒系用。此 時令聚縮合反應時間爲1 90分鐘。所得聚酯粒狀顆粒及聚 酯薄膜之特性如表2所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -53- 581777 A7 —Ξ__ 五、發明説明（51 ) [比較例1 ο ] (請先閱讀背面之注意事項再填寫本頁) 同實施例1 3進行聚縮合反應及製膜。但，將聚縮合 觸媒變更爲三氧化銻之1 · 3 %濃度乙二醇溶液，且投入量 爲4.8 3單位，另外投入安定劑用三甲基磷酸酯之2 5 %乙 二醇溶液〇 · 1 2 1單位。此時之聚縮合反應時間爲1 3 〇分鐘 〇 所得聚酯粒狀顆粒及聚酯薄膜之特性如表2所示。 [比較例1 1 ] 同實施例13進行聚縮合反應及製膜。但，將聚縮合 觸媒變更爲製造例2所得之ΤΒ溶液，且投入量爲0.129 單位。此時之聚縮合反應時間爲1 0 5分鐘。 所得聚酯粒狀顆粒及聚酯薄膜之特性如表2所示。 經濟部智慧財產局8工消費合作社印製 -54· 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 581777&quot; A7 B7 五、發明説明（52 ) 經濟部智慧財產局員工消費合作社印製 a 雛 •E- S sti k 蠢： tRrt、 S O s § g ο g d g ο 寸 r—Η Ο Km^ _ 00 01 un § ρ *......i r_·· — hJ o g o g o oo O CN OO ο ο o cn oo &gt; s wo g in g 〇 v〇 ci ο ο 异 un ¥ fi s ® OQ MD ρ cn 4Π 齡 Hs! nnn φ] 3® V〇 CN 寸· p un _ 〇 ON p i A oo O oo o g ο 〇 CN OO &gt; 异 MD 异 MD 异 wn v〇 o 闵 o cn 〇 is S Μ ^ g ^ W 1 1 1 1 〇〇 m 1 fell s W ΐ M ^ S w m cn cn cn 1 υη Ά i/S oo wS CN i/S 1 1 Orrrll 獅 讓 ΕΙΞ» 驅 v〇 1 ㈡ Oi 1 Ό 1 ㈡ 锲ε髮 PQ Η Η + m 嫠 锲 Η cn s 翠 Ιϋ 寸 τ1·1 Ή m 翠 u v〇 s 毙 w i 鎮 ο g -iJ ί 4 m m -----：---------IT------ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -55- 581777 A7 B7___ 五、發明説明（53 ) [製造例4] 製造回收之對苯二甲酸二甲酯： (請先閲讀背面之注意事項再填寫本頁) 將乙二醇200質量單位入500ml可分式燒瓶中，再 放入碳酸蘇打1.5質量單位及粉碎的瓶子等所構成之聚對 苯二甲酸乙二酯屑50質量單位，攪拌下升溫至185 °C後 ，保持該狀態4小時，使聚對苯二甲酸乙二酯屑溶解，以 結束解聚縮合反應。將所得解聚物減壓蒸餾而濃縮的同時 ，回收蒸餾餾分之乙二醇150質量單位。 將酯交換反應觸媒用碳酸蘇打〇·5質量單位及甲醇 100質量單位投入上述濃縮液中，常壓’液溫75 °C下攪拌 1小時，以進行酯交換反應。 將所得反應混合物冷卻至4 0 °C，再以玻璃製濾器過 濾。將濾器上回收之相對苯二甲酸二甲酯混合MeOH 100 質量單位後加溫至4 0 °C，攪拌後洗淨’再度以玻璃製濾 器過濾。其後重覆2次洗淨及過濾步驟。 經濟部智慧財產局員工消費合作社印製 將濾器上捕集之相對苯二甲酸二甲酯放入蒸餾裝置後 ，於壓力6.65kPa，回流比0.5之條件下進行減壓蒸餾， 再回收蒸餾餾分之對苯二甲酸二甲酯，所回收之餾分量爲 47質量單位。測定蒸餾裝置中殘餾分量，結果對苯二甲 酸二甲酯量爲2質量單位，故以投入之聚酯質量爲基準下 ，對苯二甲酸二甲酯之反應率爲93質量％。 又，蒸餾精製而回收之對苯二甲酸二甲酯中，驗出2 一羥基對苯二甲酸二甲酯0.5質量ppm。 精製回收之對苯二甲酸二甲酯品質爲，純度99.9重 -56- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A7 B7 五、發明説明（54 ) 量％以上。 (請先閱讀背面之注意事項再填寫本頁) [實施例1 7 ] 於可加壓反應之不銹鋼製容器中，將四- η- 丁基鈦 酸鹽0.008 8質量單位混入製造例4所得之對苯二甲酸二 甲酯100質量單位及乙二醇70質量單位之混合物中，於 〇.〇7MPa加壓下由140°C升溫至240°C以進行交換反應後 ，將三乙基膦基乙酸酯〇·〇35質量單位加入混合物中，以 結束酯交換反應。 其後將反應生成物移入聚合容器中，升溫至285 °C後 ，於26.67Pa以下之高真空下進行聚縮合反應，得固有粘 度0.63、二乙二醇含量1.0質量％之聚酯。 經濟部智慧財產局員工消費合作社印製 利用熔融擠押機將所得聚酯片化後，以1 8 0 °C乾燥， 再利用熔融紡絲法，由乾燥片製作絲紗支數爲 3 3 3 dtex/36fil之未延伸纖維絲條後，將其延伸4.0倍，得 絲紗支數爲 83.2 5dtex/36fil之延伸複型絲。另外，利用 製膜裝置將乾燥片熔融擠押，得未延伸薄膜後，以90 °C 分別對縱、橫方向進行延伸倍率3.5倍及4.0倍之雙軸延 伸，其後以200°C熱固定，得厚15μιη之聚酯薄膜。測定 結果表3所不。 [實施例18] 同實施例17製造聚酯樹脂，再由其製造聚酯纖維。 但，所使用之鈦化合物爲，製造例1之方法所合成的偏苯 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -57- 581777 A7 B7 五、發明説明（55 ) 三酸鈦〇.0 1 6質量單位。測定結果如表3所示。 (請先閱讀背面之注意事項再填寫本頁) [實施例19至22及比較例12至15] 實施例1 9至2 2及比較例1 2至1 5各自同實施例1 7 製造聚酯樹脂及纖維。但，所使用之鈦化合物及磷化合物 爲表3所示化合物，且依表3變更其添加量。測定結果如 表3所示，但，因比較例1 3及1 5之聚縮合反應速度較慢 ，故需200分鐘以結束聚縮合反應。 [比較例1 6 ] 將製造例4所回收之對苯二甲酸二甲酯100質量單位 及乙二醇 7〇質量單位之混合物、四一 η — 丁基鈦酸鹽 0.0 09質量單位放入可加壓反應之不銹鋼製容器後，於 0.07MPa加壓下由140°C升至240°C以進行酯交換反應， 再加入三乙基膦基乙酸酯0.04質量單位，以結束酯交換 反應。 經濟部智慧財產局員工消費合作社印製 其後將三氧化銻0.05 3單位加入反應生成物中，再將 混合物移入聚合容器，升溫至2 8 5 °C後，於2 6.6 7 P a以下 之高真空下進行聚縮合反應，得固有粘度0.63、二乙二 醇含量〇 · 9質量％之聚酯。同實施例1 7將所得聚酯纖維 化及薄膜化，測定結果如表3所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -58- 581777 A7 B7 五、發明説明（56 經濟部智慧財產局員工消費合作社印製 * 製系特性 噴嘴異 物高度 (μιη) m m m m CS) m 極限伸 度(％) CN CN CN CN m rN \〇 CN On CN) 拉伸強度 (cN/dtex) oc VC cn OC OC ON 薄膜特性 二軸延伸後 熱安定 性 0.04 0.04 0.04 0.04 0.06 0.08 無法製膜 0.06 無法製膜 0.04 &gt; 0.580 0.590 0.590 0.590 0.570 0.550 0.570 0.590 延伸前 混濁酸 (%) i_ 5 5 5 OO 5 — &lt;Π 色調 cn oo CN3 〇ΝΪ OJ cs cn rn 对· ρ 5 5 3 79.0 80.2 78.2 80.3 79.7 rn oo 111 , η oo 70.3 &gt; 0.620 0.630 0.630 0.630 0.630 ; 0.630 0.450 0.630 0.510 0.630 DEG(質 量％) ο 〇 〇 〇 〇 —· o 〇 一 ON o Sb化合 物 (SbO;毫 莫耳％) • • 1 • • ' • Μή+Μρ (毫莫耳 %) m wn m VO m OO in to 03 s VO m Mn/Mii v〇 VO r- m 5 — 磷化合物 含量 (毫莫耳 %) o to ο 〇 cn 種類 ΤΕΡΑ ΤΕΡΑ PEE ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ 含量 (毫莫耳 %) 卜 on i 讎 i 1 TBT TMT TMT TMT TMT TMT TMT TMT TMT TBT 實施例17 實施例18 實施例19 實施例21 實施例22 比較例12 比較例13 比較例14 比較例15 比較例16 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -59- 581777 A7 B7 五、發明説明（57 ) [實施例23] (請先閱讀背面之注意事項再填寫本頁) 以乙二醇將PET解聚後，利用MeOH進行酯交換反 應，得DMT後進行加水分解，得TA ( 4 - CBA、P — TA 、B A及HDT之合計量爲1 ppm以下，MMT含量爲1 50 ppm)，再將該回收之TA179質量單位及乙二醇95單位 放入預先滯留對苯二甲酸之乙二醇酯低聚物的聚縮合反應 槽內，攪拌下於氮氣中，以維持2 5 5 t，常壓之條件混合 後，得漿液，再以均一供給速度將該漿液供給聚縮合反應 槽，大氣壓下以2 7 5 °C進行4小時酯化反應，並將副產物 之水及乙二醇去除系外，直至酯化率爲98%以上，得聚合 度約5至7之低聚物。 將酯化反應所得之低聚物中22 5質量單位移入聚縮合 反應槽中，再混合聚縮合觸媒用製造例2所得之^ TT - 6 觸媒溶液」0.45質量單位。其後階段性各自將系內反應 溫度由255 °C升至 290 °C ，及將反應壓力由大氣壓減至 6 OPa，並將副產物之水及乙二醇去除系外，以進行聚縮合 反應。 經濟部智慧財產笱員工消費合作社印製 又，監控系內攪拌翼之負荷的同時，檢驗聚縮合反應 之進度，當達所希望之聚合度時結束反應。此時之聚縮合 反應時間爲1 6 0分鐘。其後由溶液擠押機之吐出口將系內 反應物連續擠成單絲狀，冷卻後切斷，得約3mm粒狀顆 业丄 私！。 另外，以1 80t將所得聚酯樹脂乾燥，再供給熔融製 膜步驟，成形爲片狀後以90t進行延伸倍率中縱3.5倍 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -60- 581777 A7 B7 _ 五、發明説明（58 ) 、橫4.0倍之雙軸延伸，再以2〇〇 t：熱固定，得厚Ι5μπι 之薄膜。 (請先閱讀背面之注意事項再填寫本頁) 所得聚酯粒狀顆粒及聚酯薄膜之特性如表4所示。 [實施例2 4 ] 同實施例23製造聚酯樹脂及聚酯薄膜。但’以製造 例3所得之「ΤΤ 一 2觸媒溶液」取代「ΤΤ 一 6觸媒溶液」 作爲聚縮合觸媒用。此時之聚縮合反應時間爲135分鐘。 所得聚酯粒狀顆粒及聚酯薄膜之特性如表4所示。 [實施例25] 同實施例23製造聚酯樹脂及聚酯薄膜。但’將「ΤΤ 一 2觸媒溶液」之投入量變更爲1 . 5 0單位。此時之聚縮 合反應時間爲1 3 5分鐘。所得聚酯粒狀顆粒及聚酯薄膜之 特性如表4所示。 [實施例26] 經濟部智慧財產局員工消費合作社印製 同實施例23製造聚酯樹脂及聚酯薄膜。但，製造例 2所得「ΤΒ溶液」及「ΤΡ - 1溶液」於不反應情形下’ 分別投入「ΤΒ溶液」0.13質量單位及「ΤΡ - 1溶液」 0.39質量單位作爲聚縮合觸媒用。此時之聚縮合反應時 間爲1 90分鐘。所得聚酯粒狀顆粒及聚酯薄膜之特性如表 4所示。 -61 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 581777 A7 B7 五、發明説明（59 ) 經濟部智慧財產局員工消費合作社印製 iH « 延伸後 熱安定性 1_ 0.03 0.04 0.07 0.04 顏色 寸· σ&lt; ON vrS 80.0 80.0 83.0 82.0 &gt; 0.580 0.580 0.550 0.540 延伸前混 濁度(％) ^ i 03 vq 4π 色調 壊 CO cn os cn - jm 79.0 81.0 81.0 81.0 &gt; 0.620 0.620 0.520 0.620 Sb化合物 (Sb2〇3) (毫莫耳％) 1 1 I 1 Μτί+Μρ (毫莫耳％)| cn m m Μρ/Μτί VO oq Ο) CS3 v〇 觸媒種 ^sO 1 CsJ 1 ν〇 1 ㈡ TB溶液 +TP1溶液 實施例23 實施例24 實施例25 實施例26 ------:----- (請先閲讀背面之注意事項再填寫本頁)[Example 12J A mixed slurry of 200 mass units of terephthalic acid and 105 mass units of ethylene glycol was placed in a reactor equipped with a stirrer, a rectification tower, and a water distillation condenser under a pressure of 270 and 0.3 MPa. An esterification reaction was performed for 240 minutes. To -48- The Benn scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A7 B7 V. Description of the invention (46) After removing half of the obtained reactants, keep the remaining half at 250 ° C, often Under pressure, 100 mass units of terephthalic acid and 52 mass units of ethylene glycol slurry were supplied to the reaction system for 150 minutes, and then an esterification reaction was performed at normal pressure for 90 minutes. During the reaction, the temperature in the reaction system was kept at 250 x :. After removing half of the obtained reactants, 100 mass units of terephthalic acid and 52 mass units of ethylene glycol slurry were similarly supplied to perform the esterification reaction, and then this step was repeated until the amount of diethylene glycol in the reactants was repeated. stable. After the amount of diethylene glycol in the reactant was stabilized, half of the reactant obtained in the esterification reaction was transferred to a polycondensation reaction device, and then the 0.018 mass unit of the acetic catalyst obtained in Preparation Example 1 and triethylphosphinoacetate 0.040 mass unit, after raising the temperature to 285 ° C, the polycondensation reaction was performed under a high vacuum below 26.67 Pa to obtain an intrinsic viscosity of 0.62, a polyester having an amount of diethylene glycol of 1.0% by mass, and the same as in the examples. 1 Manufacture of fibers. The measurement results are shown in Table 1. (Please read the notes on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -49- 581777 A7 B7 V. Description of the invention (47 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 «Cut-off characteristics Height of foreign bodies on the nozzle surface (㈣ m inch inch CN to cn inch cn m on CN pair to m limit elongation (%) ο rs OO CNJ CN IT) CN 03 On CN R OO 03 s 03 CN a OC CNJ f | oq rn OO VO cn OC… OC cn OC cn S OJ CO II \ 〇ON Unstretched film characteristics s sos 〇g O o 'CNJ p 〇sos 〇 go I cannot make a film i I cannot make a film go I cannot make a film § Cloudiness 値 CN o CN CN CsJ CN rn cn 03 cn ON — Γ Polyester polymer hue s oo οά CO o5 m cn rn p VO v〇S cn 〇S § p ρ S oi o gN p § 〇oc og OOOO ο 〇〇OOOO to oo poo cn oo o rn oo o oc ο O o &gt;: 0.620 | 0.620 1 | 0.620 | 0.620 Γ 0.600 1 | 0.600 1 0.600 0.600 0.600 [0.620 I 0.620 I 0.620 1 0.640 1 0.640 I 0.450 0.520 1 0.600 I 1 0.600 1 | 0.640] • 1 • • 1 • • 1 8 04 1 • 1 • 1 • • and _ • 1 1 Qin 1 1 • 1 • cn • 1 • 1 1 • 1 • Sb compound (Sb £ ) 3) Millimolar% • '1 1 1 1 1 • • 1 • • 1 • • • Μϋ + Μρ 1 mm wn m IT) m oc in mm vn mmm VO ms VO un On s ON CO Μγ / Μτι Mo Ear vo v〇v〇v〇 卜 VO VO cn r- vd OO — · υη rn VO 1 phosphorus compound | content (millimolar%) 沄 jo O 8 Bu type ΤΕΡΑ ΤΕΡΑ ω ω CL · ω 3: ΤΕΡΑ ΤΕΡΑ is positive Phosphate TMP TEPA I TEPA I TEPA I TEPA 1 TEPA I TEPA 1 TEPA 1 TEPA I [TEPA I 1 TEPA 1 TEPA &lt; π Λ3 content (millimolar%) mm VO m as TMT TMT TMT TMT I Titanium oxide TMT TMT TMT TMT TMT TMT TMT TMT TMT TBT Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example H Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -50- 581777 A7 B7 ______ 48) [Manufacturing example 2] (Synthetic catalyst) π Please read the precautions on the back and fill in this page.) Put 808g of ethylene glycol and 50g of acetic acid into a 2Z trinose bottle with the function of mixing and stirring solution. Mix and stir, then slowly add titanium tetrabutoxide (142 g) to obtain a transparent ethylene glycol solution of titanium compound. This solution is called "TB solution". The titanium concentration of the TB solution measured by fluorescent X-rays was 2.0%. In addition, ethylene glycol was put into a 2 "three-necked flask equipped with a function capable of heating and mixing and stirring, and triethylphosphinoacetate 2 2 g was added under stirring to obtain a transparent solution. This solution is called "TP 1 solution". Next, heat the TP 1 solution at 160 ° C, slowly add 400 g of the TB solution prepared in advance to the TP1 solution under stirring, and continue to stir at 60 ° C for 1 hour after adding the entire amount to end the titanium compound component and Reaction of phosphorus compounds. At this time, the addition ratio of the TP 1 solution and the TB solution was adjusted so that the molar ratio of the phosphorus atom to the phthalate atom was 6.0. The obtained reaction product was a solution which was soluble in ethylene glycol and had a pale yellow taste. This solution is called "TT-catalyst". [Manufacturing Example 3] The Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives) reacted with the device and sequence of Manufacturing Example 2 to obtain a catalyst. However, the adjustment of the TP 1 solution described in Manufacturing Example 2 was changed as shown below. Amount and added amount. Basically, 1 045 g of ethylene glycol was put into the same reactor as above, and 7 5 g of triethylphosphinoacetate was added under stirring to obtain a transparent solution. This solution is called "TP2 solution Secondly, heat the TP2 solution at 120 ° C, slowly add 400g of the prepared TB solution under stirring, and add 120-51 after adding the full amount-This paper size applies the Chinese national standard (CNS> A4 specification (210X297 mm) 581777 B7 V. Description of the invention (49) (Please read the precautions on the back before filling in this page) Continue stirring at ° C for 3 hours to end the reaction between the titanium compound and the phosphorus compound. At this time, the addition ratio of the TP2 solution to the TB solution It was adjusted so that the ratio of the t-ear degree to the neighboring atoms of the titanium atom was 2.0 to obtain a transparent solution. This solution was referred to as "TT-2 solution". [Example 1 3] Pre-retention ethylene glycol terephthalate While the ester oligomer reactor is being stirred, In a nitrogen atmosphere, maintaining a temperature of 2 5 ° C and a pressure of 179 units of high-purity terephthalic acid and 95 units of ethylene glycol at a uniform supply rate under normal pressure conditions, and the reaction produced the Water and ethylene glycol were distilled off, and the reaction was continued after 4 hours of esterification. At this time, the esterification rate was more than 98%, and the degree of polymerization of the resulting oligomer was about 5 to 7. 225 units of oligomer were transferred into the polycondensation reaction tank, and 0.182 units of the titanium-phosphorus reaction compound TT-6 catalyst solution described in Manufacturing Example 2 for polycondensation catalyst were mixed. Thereafter, the reaction temperature in the system was changed in stages. 2 5 5 ° C rose to 29 ° C, and after reducing the reaction pressure from atmospheric pressure to 6 OPa, the water and glycol produced by the reaction were removed, and the polycondensation reaction was performed simultaneously. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The cooperative prints and monitors the stirring wing load in the department, and checks the progress of the polycondensation reaction. When the desired degree of polymerization is reached, the reaction ends. The polycondensation reaction time at this time is 160 minutes. Thereafter, the melt spinning device The spit outlet continuously squeezes the reactants in the system It is formed into a monofilament shape and cut after cooling to obtain about 3 mm granular particles. The particles are dried at 1 80 ° C for 3 hours and then supplied to a uniaxial kneading extruder (inner diameter 65 mm, path length 1 000 mm, residence time 10 minutes), -52- This paper size will be in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A7 B7 V. Description of invention (50) (Please read the precautions on the back before filling this page) The temperature inside the machine was gradually increased from 2 80 ° C to 300 ° C for melt-kneading, and the molten polyester was extruded from the die to obtain an unstretched film. The unstretched film was biaxially stretched at a longitudinal stretch ratio of 3 · 5 times and a transverse stretch ratio of 4 · 0 times at 90 ° C, and then heat-fixed at 200 ° C to obtain a 15 μm thick film. [Example M] A polycondensation reaction and film formation were performed in the same manner as in Example 13. However, the polycondensation catalyst was changed to a titanium-phosphorus reaction compound TT-2 solution obtained in Production Example 3. The polycondensation reaction time at this time was 135 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 2. [Example 15] A polycondensation reaction was performed in the same manner as in Example 13 to obtain a polyester film. However, chloroazole blue for toner (B agent) for the amount of the target polymer was 0.3 ppm was added to the titanium-phosphorus reaction compound solution T T-6 obtained in Production Example 2. At this time, the polycondensation reaction time was set to 160 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 16] A polycondensation reaction and film formation were performed in the same manner as in Example 13. However, the TB solution and the TP1 solution obtained in Production Example 2 were put into a TB solution of 0.129 units and a TP1 solution of 0.372 units as catalyst systems without reaction. The polycondensation reaction time at this time was 190 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -53- 581777 A7 —Ξ__ V. Description of the invention (51) [Comparative Example 1 ο] (Please read the precautions on the back before filling this page) A polycondensation reaction and film formation were carried out in the same manner as in Example 13. However, the polycondensation catalyst was changed to a 1.3% strength ethylene glycol solution of antimony trioxide, and the input amount was 4.83 units. In addition, a 25% ethylene glycol solution of a trimethyl phosphate for a stabilizer was added. · 1 2 1 units. The polycondensation reaction time at this time was 130 minutes. Table 2 shows the characteristics of the obtained polyester granular particles and polyester film. [Comparative Example 1 1] A polycondensation reaction and film formation were performed in the same manner as in Example 13. However, the polycondensation catalyst was changed to the TB solution obtained in Production Example 2, and the amount of input was 0.129 units. The polycondensation reaction time at this time was 105 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 2. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the 8th Industrial Cooperative Cooperative -54 · This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 &quot; A7 B7 V. Description of the invention (52) Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed a chick • E-S sti k stupid: tRrt, SO s § g ο gdg ο inch r—Η 〇 Km ^ _ 00 01 un § ρ * ...... i r_ ·· — hJ ogogo oo O CN OO ο ο o cn oo &gt; s wo g in g 〇v〇ci ο ο isoun ¥ fi s ® OQ MD ρ cn 4Π age Hs! Nnn φ] 3® V〇CN inch · p un _ 〇ON pi A oo O oo og ο CN OO &gt; different MD different MD different wn v〇o Min o cn 〇is S Μ ^ g ^ W 1 1 1 1 〇〇m 1 fell s W ΐ M ^ S wm cn cn cn 1 υη Ά i / S oo wS CN i / S 1 1 Orrrll 让 让 ΕΙΞ »DRIVE v〇1 ㈡ Oi 1 Ό 1 ㈡ 发 ε 发 PQ Η Η + m 嫠 锲 Η cn s Cui 1ϋ inch τ1 · 1 Ή m翠 uv〇s 毙 wi town ο g -iJ ί 4 mm -----: --------- IT ------ (Please read the precautions on the back before filling this page) This Paper size applies to China National Standard (CNS) A4 (210X297) ) -55- 581777 A7 B7___ 5. Description of the invention (53) [Manufacturing example 4] Manufacture of recovered dimethyl terephthalate: (Please read the precautions on the back before filling this page) 200 mass units of ethylene glycol Put it into a 500ml separable flask, and put 50 mass units of polyethylene terephthalate shavings composed of 1.5 mass units of carbonated soda and crushed bottles, etc., and keep the temperature after stirring to 185 ° C. 4 Hours, the polyethylene terephthalate crumbs were dissolved to end the depolymerization condensation reaction. The obtained depolymer was concentrated by distillation under reduced pressure, and 150 mass units of ethylene glycol in the distillation fraction were recovered. The transesterification catalyst was charged with 0.5 mass units of carbonated soda and 100 mass units of methanol into the above-mentioned concentrated solution, and stirred at 75 ° C at normal pressure for 1 hour to carry out the transesterification reaction. The resulting reaction mixture was cooled to 40 ° C and then filtered through a glass filter. The relative dimethyl phthalate recovered on the filter was mixed with 100 mass units of MeOH and heated to 40 ° C. After stirring, it was washed and washed again, and filtered through a glass filter. Thereafter, the washing and filtering steps were repeated twice. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, put the relative dimethyl phthalate captured on the filter into the distillation device, and perform vacuum distillation at a pressure of 6.65kPa and a reflux ratio of 0.5, and then recover the distillation fraction. The recovered distillate was 47 mass units of dimethyl terephthalate. The residual fraction in the distillation apparatus was measured. As a result, the amount of dimethyl terephthalate was 2 mass units. Therefore, the reaction rate of dimethyl terephthalate was 93% by mass based on the mass of the polyester charged. Further, in the dimethyl terephthalate recovered by distillation and purification, 0.5 mass ppm of dimethyl monoterephthalate was detected. The quality of refined dimethyl terephthalate is 99.9 weight -56- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A7 B7 V. Description of invention (54) Amount above . (Please read the precautions on the back before filling in this page) [Example 17] In a stainless steel container that can be pressurized, tetra-n-butyl titanate 0.008 8 mass units were mixed into the product obtained in Production Example 4. In a mixture of 100 mass units of dimethyl terephthalate and 70 mass units of ethylene glycol, the temperature was raised from 140 ° C to 240 ° C under a pressure of 0.07 MPa to perform an exchange reaction. Acetate 0.035 mass unit was added to the mixture to end the transesterification reaction. Thereafter, the reaction product was transferred into a polymerization vessel, and the temperature was raised to 285 ° C, and then the polycondensation reaction was performed under a high vacuum below 26.67 Pa to obtain a polyester having an inherent viscosity of 0.63 and a diethylene glycol content of 1.0% by mass. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The melted extruder was used to flake the obtained polyester sheet, dried at 180 ° C, and then the melt spinning method was used to make silk yarn counts from the dried sheet to 3 3 3 After dtex / 36fil unstretched fiber yarn, it was stretched 4.0 times to obtain a stretched composite yarn with a yarn count of 83.2 5dtex / 36fil. In addition, the dry sheet was melted and extruded using a film-forming device to obtain an unstretched film, and the biaxial stretching was performed at 90 ° C in the longitudinal and horizontal directions at a stretching ratio of 3.5 times and 4.0 times, and then heat-fixed at 200 ° C. To obtain a 15 μm thick polyester film. The measurement results are shown in Table 3. [Example 18] A polyester resin was produced in the same manner as in Example 17, and polyester fibers were produced therefrom. However, the titanium compound used is the standard benzene sheet paper synthesized by the method of Manufacturing Example 1 to the Chinese National Standard (CNS) A4 specification (210X297 mm) -57- 581777 A7 B7 V. Description of the invention (55) Titanate 0.06 mass unit. The measurement results are shown in Table 3. (Please read the precautions on the back before filling in this page) [Examples 19 to 22 and Comparative Examples 12 to 15] Examples 1 9 to 2 2 and Comparative Examples 1 2 to 1 5 are the same as those in Example 1 7 Resin and fiber. However, the titanium compounds and phosphorus compounds used are the compounds shown in Table 3, and the added amounts are changed in accordance with Table 3. The measurement results are shown in Table 3. However, since the polycondensation reaction rates of Comparative Examples 13 and 15 were slow, it took 200 minutes to end the polycondensation reaction. [Comparative Example 16] A mixture of 100 mass units of dimethyl terephthalate and 70 mass units of ethylene glycol, and tetra-n-butyl titanate 0.0 09 mass units were collected in Production Example 4. After the stainless steel container was pressurized, the temperature was raised from 140 ° C to 240 ° C under a pressure of 0.07 MPa to perform a transesterification reaction, and then 0.04 mass unit of triethylphosphinoacetate was added to terminate the transesterification reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and then adding 0.05 3 units of antimony trioxide to the reaction product, and then moving the mixture into a polymerization vessel, and raising the temperature to 2 8 5 ° C, which is as high as 2 6.6 7 P a The polycondensation reaction was performed under vacuum to obtain a polyester having an inherent viscosity of 0.63 and a diethylene glycol content of 0.9% by mass. The obtained polyester was fiberized and thinned in the same manner as in Example 17. The measurement results are shown in Table 3. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -58- 581777 A7 B7 V. Description of the invention (56 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * System characteristics Nozzle foreign body height (μιη) mmmm CS) m Ultimate elongation (%) CN CN CN CN m rN \ 〇CN On CN) Tensile strength (cN / dtex) oc VC cn OC OC ON Film characteristics Thermal stability after biaxial stretching 0.04 0.04 0.04 0.04 0.06 0.08 Cannot form 0.06 Cannot form 0.04 &gt; 0.580 0.590 0.590 0.590 0.570 0.550 0.570 0.590 Turbid acid before stretching (%) i_ 5 5 5 OO 5 — &lt; Π Hue cn oo CN3 〇ΝΪ OJ cs cn rn Pair · ρ 5 5 3 79.0 80.2 78.2 80.3 79.7 rn oo 111, η oo 70.3 &gt; 0.620 0.630 0.630 0.630 0.630; 0.630 0.450 0.630 0.510 0.630 DEG (% by mass) ο 〇〇〇〇〇— · o 〇ON ON Sb compound (SbO; millimole Ear%) • • 1 • • 'Μή + Μρ (millimolar%) m wn m VO m OO in to 03 s VO m Mn / Mii v〇VO r- m 5 — phosphorus compound content (millimolar% ) o to ο 〇cn Type T ΕΡΑ ΤΕΡΑ PEE ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΕΡΑ ΤΡΑ content (millimolar%) buon i 雠 i 1 TBT TMT TMT TMT TMT TMT TMT TMT TMT TBT Example 17 Example 18 Example 19 Example 19 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 (Please read the precautions on the back before filling in this page) This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -59- 581777 A7 B7 5 Explanation of the invention (57) [Example 23] (Please read the precautions on the back before filling this page) After depolymerizing PET with ethylene glycol, use MeOH for transesterification reaction to obtain DMT and hydrolyze to obtain TA (4-The total amount of CBA, P — TA, BA and HDT is less than 1 ppm, and the MMT content is 1 50 ppm.) Then put the recovered TA179 mass unit and 95 units of ethylene glycol into pre-retained terephthalic acid In a polycondensation reaction tank of ethylene glycol ester oligomer, stirring under nitrogen to maintain 2 5 5 t under normal pressure conditions to obtain a slurry. The slurry is then fed to the polycondensation reaction at a uniform supply rate.The esterification reaction was carried out at 27 5 ° C for 4 hours under atmospheric pressure, and the by-product water and ethylene glycol were removed until the esterification rate was above 98%, and an oligomer with a polymerization degree of about 5 to 7 was obtained. . 225 mass units of the oligomer obtained by the esterification reaction were transferred into a polycondensation reaction tank, and ^ TT-6 catalyst solution obtained in Production Example 2 for the polycondensation catalyst was mixed with 0.45 mass units. Thereafter, the reaction temperature in the system was increased from 255 ° C to 290 ° C in stages, and the reaction pressure was reduced from atmospheric pressure to 6 OPa, and water and ethylene glycol by-products were removed from the system to perform the polycondensation reaction. . Printed by the Intellectual Property of the Ministry of Economic Affairs and Employees' Cooperatives. In addition, while monitoring the load of the stirring wing in the system, the progress of the polycondensation reaction is checked, and the reaction ends when the desired degree of polymerization is reached. The polycondensation reaction time at this time was 160 minutes. After that, the reactant in the system was continuously extruded into a monofilament shape from the discharge port of the solution extruder, and then cut after cooling to obtain about 3mm granular particles. . In addition, the obtained polyester resin was dried at 1 80t, and then supplied to the melting film forming step. After being formed into a sheet, the stretching ratio was 3.5 times in the vertical direction at 90 t. -60- 581777 A7 B7 _ 5. Description of the invention (58), biaxial extension of 4.0 times horizontal, and then fixed by 200t: heat, to obtain a film of thickness 15μm. (Please read the precautions on the back before filling this page) The properties of the obtained polyester granules and polyester film are shown in Table 4. [Example 2 4] A polyester resin and a polyester film were produced in the same manner as in Example 23. However, the "TT-2 catalyst solution" obtained in Manufacturing Example 3 was used instead of the "TT-6 catalyst solution" as a polycondensation catalyst. The polycondensation reaction time at this time was 135 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 4. [Example 25] A polyester resin and a polyester film were produced in the same manner as in Example 23. However, the amount of "TT-2 catalyst solution" was changed to 1.5 units. The polymerization reaction time at this time was 135 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 4. [Example 26] Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The same as Example 23 was used to produce polyester resin and polyester film. However, in the case of "TB solution" and "TP-1 solution" obtained in Production Example 2 under non-reaction conditions, 0.13 mass units of "TB solution" and 0.39 mass units of "TP-1 solution" were used as polycondensation catalysts, respectively. The polycondensation reaction time at this time was 1 90 minutes. The properties of the obtained polyester granular particles and polyester film are shown in Table 4. -61-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 581777 A7 B7 V. Description of the invention (59) Printed by iH printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs «Thermal stability after extension 1_ 0.03 0.04 0.07 0.04 Color inch σ &lt; ON vrS 80.0 80.0 83.0 82.0 &gt; 0.580 0.580 0.550 0.540 Haze before stretching (%) ^ i 03 vq 4π Hue 壊 CO cn os cn-jm 79.0 81.0 81.0 81.0 &gt; 0.620 0.620 0.520 0.620 Sb Compound (Sb2〇3) (millimol%) 1 1 I 1 Μτί + Μρ (millimol%) | cn mm Μρ / Μτί VO oq 〇) CS3 v〇 catalyst species ^ sO 1 CsJ 1 ν〇1 ㈡ TB solution + TP1 solution Example 23 Example 24 Example 25 Example 26 ------: ----- (Please read the precautions on the back before filling this page)

、1T 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -62- 581777 A7 B7 五、發明説明（6〇) [實施例2 7 ] ---------— (請先閲讀背面之注意事項再填寫本頁) 將對苯二甲酸二甲酯1〇〇質量單位及乙二醇70質量 單位之混合物、四一 η-丁基鈦酸鹽0.009質量單位放入 可加壓反應之SUS製容器中，於〇.〇7MPa加壓下將混合 物由140°C升至240 °C以進行酯交換反應，其後加入單一 —η—丁基磷酸酯0.031質量單位，以結束酯交換反應。 將反應生成物移入聚合容器中，升溫至2 9 0 °C後，於 30Pa以下之高真空下進行聚縮合反應，得固有粘度〇.63 、二乙二醇含量1 · 3質量％之聚酯樹脂。 利用熔融造粒機將所得聚酯樹脂片化後乾燥，再將乾 燥片供給溶融結絲步驟，得絲紗支數爲 3 3 3 d t e X / 3 6 f i 1之 未延伸纖維，其後將其延伸 4.0倍，得絲紗支數爲 83.25dtex/36fil之延伸複型絲。 測定結果如表5所示。 Φ! [實施例28] 經濟部智慧財產局員工消費合作社印製 同實施例2 7製造聚酯樹脂及聚酯纖維。但，將鈦化 合物變更爲製造例1之方法合成而得的偏苯三酸鈦0.016 質量單位。測定結果如表5所示。 [實施例29至33及比較例17至22] 實施例29至33及比較例17至22各自同實施例27 製造聚酯樹脂及聚酯纖維。但，所使用之鈦化合物及磷 化合物如表5所示，且添加量如表5所示。測定結果如 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -63· 581777 A7 ------- -B7 五、發明説明（61 ) _ 5所示。 [實施例3 4 ] (請先閱讀背面之注意事項再填寫本頁) 同實施例2 7製造聚酯樹脂及聚酯纖維。但，將鈦化 合物及磷化合物變更爲表5所示化合物，且添加量如表5 所示’又’酯交換反應結束後加入2 0質量％氧化鈦之乙 二醇漿液1 · 5質量單位。測定結果如表5所示。 [實施例3 5 ] 同實施例27製造聚酯樹脂及聚酯纖維，但，酯交換 反應結束後，將季戊四醇一四[3 -（3,5—二一 tert- 丁基 一 4一羥基苯基）丙酸酯](吉巴斯公司製，商標名：伊魯 卡1010) 0.02質量單位加入所得反應生成物中。測定結 果如表5所示。 [比較例2 3 ] 經濟部智慧財產局員工消費合作社印製 將對苯二甲酸二甲酯100質量單位及乙二醇70質量 單位之混合物、四—η-丁基鈦酸鹽0.009質量單位放入 可加壓反應之SUS製容器中，於0.07MPa加壓下將混合 物由140 °C升至240 °C以進行酯交換反應，其後加入單—η —丁基磷酸酯0.031質量單位，以結束酯交換反應。 其次將三氧化銻0.05 3質量單位加入反應生成物中， 再移入聚合容器中，升溫至290°C後，於30Pa以下之高 真空下進行聚縮合反應，得固有粘度0.63、二乙二醇含 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） • 64 - 581777 A7 B7 五、發明説明（62 ) 量1 . 3質量％之聚酯。同實施例2 7將該聚酯樹脂熔融紡 絲，再供給延伸步驟，得聚酯纖維。測定結果如表5所示 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -65- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 581777、 1T This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -62- 581777 A7 B7 V. Description of the invention (60) [Example 2 7] ---------— ( (Please read the precautions on the back before filling out this page) Put a mixture of dimethyl terephthalate 100 mass units and ethylene glycol 70 mass units, and tetra-n-butyl titanate 0.009 mass units into the In a SUS container under pressure, the mixture was raised from 140 ° C to 240 ° C under a pressure of 0.07 MPa for transesterification reaction, and then a single-η-butyl phosphate 0.031 mass unit was added to The transesterification reaction is ended. The reaction product was transferred into a polymerization vessel, and the temperature was raised to 290 ° C, and then the polycondensation reaction was performed under a high vacuum of 30 Pa or less. A polyester having an inherent viscosity of 0.63 and a diethylene glycol content of 1.3% by mass was obtained. Resin. The obtained polyester resin was pelletized by a melt granulator and dried, and then the dried sheet was supplied to the step of melting and fusing to obtain unstretched fibers having a yarn count of 3 3 3 dte X / 3 6 fi 1 and thereafter Extending 4.0 times, the yarn with the yarn count of 83.25dtex / 36fil was obtained. The measurement results are shown in Table 5. Φ! [Example 28] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Same as Example 2 7 Manufacture of polyester resin and polyester fiber. However, the titanium compound was changed to 0.016 mass unit of titanium trimellitate synthesized by the method of Production Example 1. The measurement results are shown in Table 5. [Examples 29 to 33 and Comparative Examples 17 to 22] Each of Examples 29 to 33 and Comparative Examples 17 to 22 was the same as Example 27 to produce a polyester resin and a polyester fiber. However, the titanium compounds and phosphorus compounds used are shown in Table 5, and the added amounts are shown in Table 5. The measurement results are as shown in the paper standard applicable to China National Standard (CNS) A4 (210X297 mm) -63 · 581777 A7 ------- -B7 V. Description of the invention (61) _5. [Example 3 4] (Please read the precautions on the back before filling in this page) The same as Example 2 7 Manufacture of polyester resin and polyester fiber. However, the titanium compound and the phosphorus compound were changed to the compounds shown in Table 5, and the amount of addition was as shown in Table 5. After the completion of the transesterification reaction, 20% by mass of titanium oxide in ethylene glycol slurry 1.5 mass units were added. The measurement results are shown in Table 5. [Example 3 5] A polyester resin and polyester fiber were produced in the same manner as in Example 27, but after the transesterification reaction was completed, pentaerythritol tetrakid [3-(3,5-ditert-butyl-4-hydroxybenzene Base) propionate] (manufactured by Gibbs Corporation, brand name: Iluka 1010) 0.02 mass unit was added to the obtained reaction product. The measurement results are shown in Table 5. [Comparative Example 2 3] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, a mixture of 100 mass units of dimethyl terephthalate and 70 mass units of ethylene glycol, and 0.009 mass units of tetra-n-butyl titanate Into a SUS container that can be pressurized, the mixture was raised from 140 ° C to 240 ° C under a pressure of 0.07 MPa for transesterification reaction, and then 0.031 mass unit of mono-η-butyl phosphate was added. The transesterification reaction is ended. Secondly, antimony trioxide 0.05 3 mass units were added to the reaction product, and then transferred to a polymerization container. After heating to 290 ° C, the polycondensation reaction was performed under a high vacuum of 30 Pa or less, and the intrinsic viscosity was 0.63. This paper size applies Chinese National Standard (CNS) A4 (210X29 * 7mm) • 64-581777 A7 B7 V. Description of the invention (62) 1.3% by mass polyester. This polyester resin was melt-spun in the same manner as in Example 2 and then supplied to the drawing step to obtain a polyester fiber. The measurement results are shown in Table 5 (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-65- This paper size applies to China National Standard (CNS) A4 (210X29 * 7mm) Centimeter) 581777

A B 五、發明説明（63) 經濟部智慧財產局員工消費合作社印製 製系特性 噴嘴異 物高度 (μηι) — CN — m CN CN — m 寸 — Oi m — 極限伸 度 (%) οο rsi oo Csl CNI ON CSI CNj \D CSJ oc CNJ CN cn csi CNI 固有粘 度 0.611 0.612 0.61 0.613 0.608 0.611 0.612 0.611 0.62 0.607 0.44 0.608 0.498 0.529 0.505 0.622 拉伸強度 (c N/d te X) ΟΟ 〇〇 OO OO 〇\ ON c-i CNl cn cn On 色調 4D oo m cn cvi m cn 寸 WO Oi m — 二 一 cs CNJ υη CNl g 79.5 79.5 gN g 79.5 wn 80.2 r- CNl oo oo oo g 〇 DEG (質量 %) rn cn 寸· cn 寸· rn rn 二 cn ON rn cn 对· On m &gt; 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.45 I 0.63 ! wn 0.54 0.52 0.63 防氧化 劑(ppm) 1 1 1 1 1 1 1 1 〇 cs t 1 1 1 1 1 1 氧化鈦 (質量 %) 1 1 1 1 1 1 1 CO 1 1 1 1 1 1 1 1 Mti+Mp (毫莫耳 %) to C^) m cn wn CNI wn m CsJ cn m o , 1 &lt; r-H o ON g OO υη m Μρ/Μπ cn 对 寸 一 OO m· r—( un rn Sb化合 物 (Sb2〇3) (毫莫耳 %) 1 1 1 1 唯 • 1 1 1 1 1 • • 1 1 磷化合物 含量 (毫莫 耳％) o o § 8 種類 MBP MBP MBP 1- MBP MBP PPA THEP MBP MBP MBP MBP MBP MBP MBP MBP MBP Μ 含量 (毫莫 耳％) r- v/n CN i 種類 1 i TBT -1 TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TBT 實施例27 實施例28 實施例29 實施例30 實施例31 實施例32 實施例33 實施例34 實施例35 比較例17 比較例18 比較例19 比較例20 比較例21 比較例221 比較例23 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -66 - 58I777 A7 B7 五、發明説明（64 ) 產業上利用可能性 本發明聚酯樹脂之製造方法可有效率地製造具有良好 透明性及色調、高熱熔融安定性之聚酯樹脂，又，本發明 之聚酯樹脂、聚酯纖維、聚酯薄膜及聚酯瓶狀成形物均具 有良好透明性及色調，且實用上可有效率製造。 (請先閲讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -67-AB V. Description of invention (63) Characteristics of nozzle foreign body height (μηι) — CN — m CN CN — m inch — Oi m — limit elongation (%) οο rsi oo Csl CNI ON CSI CNj \ D CSJ oc CNJ CN cn csi CNI Intrinsic viscosity 0.611 0.612 0.61 0.613 0.608 0.611 0.612 0.611 0.62 0.607 0.44 0.608 0.498 0.529 0.505 0.622 Tensile strength (c N / d te X) 〇 〇OOOO OO \ ON ci CNl cn cn On Hue 4D oo m cn cvi m cn inch WO Oi m — two one cs CNJ υη CNl g 79.5 79.5 gN g 79.5 wn 80.2 r- CNl oo oo oo g 〇DEG (mass%) rn cn inch cn Inch · rn rn two cn ON rn cn pair · On m &gt; 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.45 I 0.63! Wn 0.54 0.52 0.63 Antioxidant (ppm) 1 1 1 1 1 1 1 1 1 〇cs t 1 1 1 1 1 1 Titanium oxide (% by mass) 1 1 1 1 1 1 1 1 CO 1 1 1 1 1 1 1 1 1 Mti + Mp (millimolar%) to C ^) m cn wn CNI wn m CsJ cn mo, 1 &lt; rH o ON g OO υη m Μρ / Μπ cn pair inch OO m · r— (un rn Sb compound (Sb203) (Millimol%) 1 1 1 1 Only • 1 1 1 1 1 • • 1 1 Phosphorus compound content (millimol%) oo 8 types MBP MBP MBP 1- MBP MBP PPA THEP MBP MBP MBP MBP MBP MBP MBP MBP MBP MBP Μ content (millimolar%) r-v / n CN i type 1 i TBT -1 TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TBT Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Comparative example 17 Comparative example 18 Comparative example 19 Comparative example 20 Comparative example 21 Comparative example 221 Comparative example 23 (Please read the precautions on the back before filling this page) Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -66-58I777 A7 B7 V. Description of invention (64) Industrial utilization possibility The method for manufacturing the polyester resin of the present invention can be efficiently manufactured with good transparency Polyester resin with high color stability, high heat melting stability, and the polyester resin, polyester fiber, polyester film, and polyester bottle-shaped article of the present invention all have good transparency and color tone, and can be effectively used in practice Manufacturing. (Please read the precautions on the back before filling this page) • Binding and printing Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm) -67-

Claims (1)

581777 A8 B8 C8 D8 2 六、申請專利範圍 未反應混合物（III)爲 鈦化合物成分（1 )與，（2b )含有下列一般式（2 )或（ 3 )： (R4 )n —（〇)P —P—（〇h)3-II 0 (2) [式（2)中，R4爲含2至18個碳原子之烷基或含6至20 個碳原子之芳基；η爲1或2之整數，又，η爲1時，p 爲0或1之整數，η爲2時，ρ爲〇] 0(CH2CH2 H — (0 — CH2 CH2 )&quot; — 〇— P—0—（CH2 CH2 — 0&gt;τγΗ (3 ) (請先閲讀背面之注意事項再填寫本頁) ο [式（3)中，m、ma及mb各自獨立爲1或2之整數] 所示至少一種磷化合物之磷化合物成分的未反應混合物 且觸媒系爲符合下列式（a ) 、（ b )及（c )要件： 經濟部智慧財產局員工消費合作社印製 2 ^ MTi ^ 1 5 (a ) 1 ^ ( Mp/Mii )^15 (b) 10^ ( Mii + Mp )^100 (c ) [式（a) ( b) ( c)中，MTi爲觸媒系所含鈦元素之毫莫 耳量對聚（芳香族二羧酸乙二酯）中芳香族二羧酸乙二酯 重覆單位之總莫耳量的比値，Mp爲觸媒系所含磷元素之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -69 - 581777 A8 B8 C8 D8 六、申請專利範圍° 毫莫耳量對聚（芳香族二羧酸乙二酯）中芳香族二羧酸乙 二酯重覆單位之總莫耳量的比値]。 (請先閲讀背面之注意事項再填寫本頁) 2.如申請專利範圍第1項之製造方法，其中係利用芳 香族二羧酸與乙二醇之二酯化反應，製造芳香族二羧酸及 乙二醇之二酯。 3 .如申請專利範圍第1項之製造方法，其中係利用芳 香族二羧酸之二烷基酯與乙二醇的酯交換反應，製造芳香 族二羧酸及乙二醇之二酯。 4.如申請專利範圍第3項之製造方法，其中係於至少 存在觸媒系中未反應或反應之鈦化合物成分（1)下，進 行芳香族二羧酸之二烷基酯與乙二醇的酯交換反應後，於 存在含有至少已含有的未反應或反應之鈦化合物成分 )，及未反應或反應之磷化合物成分（2a)，或未反應之 磷化合物成分（2b )的觸媒下，使酯交換反應所得之含芳 香族二羧酸及乙二酯之二酯的反應混合物聚縮合。 經濟部智慧財產局員工消費合作社印製 5 .如申請專利範圍第1至4項中任一項之製造方法， 其中芳香族二羧酸爲，對苯二甲酸、間苯二甲酸、萘二殘 酸、5 —磺基間苯二甲酸金屬鹽及5 —磺基間苯二甲酸鐵 鹽中所選出。 6 ·如申請專利範圍第3或4項之製造方法，其中芳香 族二羧酸之二烷基酯爲，對苯二甲酸二甲酯、間苯二甲酸 二甲酯、萘二甲酸二甲酯、對苯二甲酸二乙酯、間苯二甲 酸二乙酯及萘二甲酸二乙酯中所選出。 7.如申請專利範圍第1項之製造方法，其中鈦化合物 本紙張尺度適用中國國家標準（CNS ) A4規格（21 〇X：297公釐) ^7〇1 -^ ---- 581777 AS BS C8 t&gt;8 六、申請專利範圍4 成分（1 )用鈦烷氧化物爲，下列一般式（4 r 0R€ R5 — 0- -Ti 一 0- OR7 -R8 (4) [式（4)中，R5、R6、R7及R8各自獨立爲含2至10個碳 原子之烷基或苯基；m。爲lg 4之整數] 所示鈦化合物中所選出。 8.如申請專利範圍第1項之製造方法，其中鈦化合物 成分（1)用芳香族多價羧酸爲’下列一般式（5): Qr (C00H)r (5 ) 經濟部智慧財產局員工消費合作社印製 [式（5)中，na爲2至4之整數] 所示化合物中所選出。 9·如申請專利範圍第3項之製造方法，其中係於〇.〇5 至0.2OMPa加壓下進行酯交換反應。 10.如申請專利範圍第3項之製造方法，其中供給酯 交換反應用芳香族羧酸之二烷基酯爲，對全部莫耳量含有 80莫耳％以上之對苯二甲酸二甲酯。 1 1.如申請專利範圍第3項之製造方法，其中供給醋 交換反應用芳香族羧酸二烷基酯全量之70莫耳：％以上爲 ，將聚對苯二甲酸烷二酯解聚而回收之對苯二甲酸二院酯 (請先閲讀背面之注意事項再填寫本頁)581777 A8 B8 C8 D8 2 VI. Patent application scope The unreacted mixture (III) is a titanium compound component (1) and (2b) contains the following general formula (2) or (3): (R4) n — (〇) P —P— (〇h) 3-II 0 (2) [In the formula (2), R 4 is an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms; η is 1 or 2 Integer, and when η is 1, p is an integer of 0 or 1. When η is 2, ρ is 0] 0 (CH2CH2 H — (0 — CH2 CH2) &quot; — 〇— P—0— (CH2 CH2 — 0 &gt; τγΗ (3) (Please read the precautions on the back before filling this page) ο [in formula (3), m, ma and mb are each independently an integer of 1 or 2] The unreacted mixture of compounds and the catalyst are in accordance with the following formulae (a), (b) and (c): Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 ^ MTi ^ 1 5 (a) 1 ^ (Mp / Mii) ^ 15 (b) 10 ^ (Mii + Mp) ^ 100 (c) [In the formula (a) (b) (c), MTi is the millimolar convolution of the titanium element contained in the catalyst system ( Aromatic ethylene dicarboxylate) In aromatic ethylene dicarboxylic acid repeat unit Molar ratio, Mp is the paper size of the phosphorus element contained in the catalyst system. Applicable to Chinese National Standard (CNS) A4 (210X297 mm) -69-581777 A8 B8 C8 D8 6. Application scope ° The ratio of the amount of ears to the total moles of aromatic dicarboxylic acid repeating units in poly (aromatic dicarboxylic acid ethylene glycol). (Please read the precautions on the back before filling this page) 2 The manufacturing method according to item 1 of the scope of patent application, wherein the diesterization reaction of aromatic dicarboxylic acid and ethylene glycol is used to manufacture the diester of aromatic dicarboxylic acid and ethylene glycol. 3. If the scope of patent application is The manufacturing method of item 1 is to use a transesterification reaction of a dialkyl ester of an aromatic dicarboxylic acid with ethylene glycol to produce a diester of an aromatic dicarboxylic acid and ethylene glycol. The manufacturing method of 3, wherein the transesterification reaction of a dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol is performed in the presence of at least a titanium compound component (1) which is not reacted or reacted in the catalyst system, and then (Presence of at least unreacted or reacted titanium compounds) A reaction mixture containing an aromatic dicarboxylic acid and a diester of ethylene glycol obtained by a transesterification reaction with a catalyst of unreacted or reacted phosphorus compound component (2a) or unreacted phosphorus compound component (2b) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. The manufacturing method according to any one of the claims 1 to 4, wherein the aromatic dicarboxylic acid is terephthalic acid, isophthalic acid, Naphthalene diresidual acid, metal 5-sulfoisophthalate, and iron 5-sulfoisophthalate. 6. The manufacturing method according to item 3 or 4 of the scope of patent application, wherein the dialkyl ester of the aromatic dicarboxylic acid is dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate , Diethyl terephthalate, diethyl isophthalate, and diethyl naphthalate. 7. The manufacturing method according to item 1 of the scope of patent application, in which the titanium compound's paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 0X: 297 mm) ^ 7〇1-^ ---- 581777 AS BS C8 t &gt; 8 6. Scope of patent application 4 The component (1) uses titanium alkoxide as the following general formula (4 r 0R € R5 — 0- -Ti-0- OR7 -R8 (4) [in formula (4) , R5, R6, R7, and R8 are each independently an alkyl or phenyl group containing 2 to 10 carbon atoms; m. Is an integer of lg 4] is selected from the titanium compounds shown in the figure. The manufacturing method, wherein the titanium compound component (1) uses an aromatic polyvalent carboxylic acid as the following general formula (5): Qr (C00H) r (5) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Formula (5) Wherein, na is an integer of 2 to 4] is selected from the compounds shown in 9.] The manufacturing method according to item 3 of the scope of patent application, wherein the transesterification reaction is performed under a pressure of 0.05 to 0.20 MPa. 10. For example, the manufacturing method of the third scope of the patent application, wherein the dialkyl ester of the aromatic carboxylic acid used for the transesterification reaction is 80 mol for the entire mol amount The above dimethyl terephthalate. 1 1. The production method according to item 3 of the patent application scope, wherein the total amount of the aromatic carboxylic acid dialkyl ester used for the vinegar exchange reaction is 70 mol:% or more, Dialkyl terephthalate recovered by depolymerization of alkyl terephthalate (please read the precautions on the back before filling this page) -71 - 581777 A8 B8 C8 D8 六、申請專利範圍5 〇 (請先閲讀背面之注意事項再填寫本頁) 1 2 ·如申請專利範圍第1 1項之製造方法，其中將回收 之對苯二甲酸二烷酯中2 —羥基對苯二甲酸含量控制於 2ρρηι以下。 1 3 ·如申請專利範圍第4項之製造方法，其中觸媒系 係由鈦化合物成分（1 )與磷化合物成分（2a )或（2b ) 之未反應混合物所構成， 又，係於酯交換反應開始前或開始時，將鈦化合物成 分（1)全量加入反應系中， 係於聚縮合反應開始前或開始時，將磷化合物成分（ 2a)或（2b)全量加入酯交換反應所得之反應系中。 1 4 ·如申請專利範圍第4項之製造方法，其中觸媒系 係由鈦化合物成分（1 )與磷化合物成分（2a )之反應生 成物所構成，且於酯交換反應開始前或開始時，將全量力口 入反應系中， 又，結束酯交換反應後，將反應混合物供給聚縮合反 應。 經濟部智慧財產局員工消費合作社印製 15.如申請專利範圍第4項之製造方法，其中係於醋 交換反應前，將部分鈦化合物成分（1 )、部分鈦化合物 成分（1 )與磷化合物成分（2a )之反應生成物或部分磷 化合物成分（2a )加入反應系中，又，於酯交換反應途中 或結束後，及聚縮合反應前或途中至少一階段中，將殘餘 部分加入反應系中。 1 6.如申請專利範圍第2項之製造方法，其中係於二 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-72 - 581777 A8 B8 C8 D8 六、申請專利範圍6 (請先閣讀背面之注意事項再填寫本頁) 酯化反應前，將磷化合物成分（2a )全量加入二酯化反應 系中，或於二酯化反應前添加部分磷化合物成分（2 a )， 再於二酯化反應途中或結束後，及聚縮合反應前或途中至 少一階段中，將殘餘部分加入反應系中。 17.—種聚（芳香族二羧酸乙二酯）樹脂，其特徵爲 ，利用如申請專利範圍第1至1 6項中任一項之聚（芳香 族二羧酸乙二酯）樹脂製方法製造者。 i 8 .如申請專利範圍第1 7項之聚（芳香族二羧酸乙二 酯）樹脂，其中另含有1重量％以下之阻胺苯酚系防氧化 劑。 19. 如申請專利範圍第1項之製造方法，其中將聚（ 芳香族二羧酸乙二酯）樹脂所含銻元素及鍺元素之含量各 自控制於5/1 000莫耳％以下。 20. —種聚酯纖維，其特徵爲，含有如申請專利範圍 第1 7項至1 9項中任一項之聚（芳香族二羧酸乙二酯）樹 脂。 21如申請專利範圍第20項之聚酯纖維，其中聚（芳 香族二羧酸乙二酯）樹脂之主成分爲聚對苯二甲酸乙二酯 經濟部智慧財產局員工消費合作社印製 〇 22·—種聚酯薄膜，其特徵爲，含有如申請專利範圍 第17至19項中任一項之聚（芳香族二羧酸乙二酯）樹月旨 〇 23.如申請專利範圍第22項之聚酯薄膜，其中聚（芳 香族二羧酸乙二酯）樹脂之主成分爲聚對苯二甲酸乙二醋 -73- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 581777 A8 B8 C8 D8 六、申請專利範圍7 〇 2 4.—種瓶狀聚酯成形物，其特徵爲，含有如申請專 利範圍第1 7項至1 9項中任一項之聚（芳香族二羧酸乙二 酯）樹脂。 25.如申請專利範圍第24項之瓶狀聚酯成形物，其中 聚（芳香族二羧酸乙二酯）樹脂之主成分爲聚對苯二甲酸 乙二酯。 ϊ I. —I— ........ j I n (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公釐） _ 74 - 號專利年ρ靑案 附件’·-71-581777 A8 B8 C8 D8 6. Scope of patent application 5 〇 (Please read the precautions on the back before filling out this page) 1 2 · If you apply for the manufacturing method of item 11 in the scope of patent application, which will be recycled The content of 2-hydroxyterephthalic acid in dialkyl formate is controlled below 2ρρηι. 1 3 · The manufacturing method according to item 4 of the scope of the patent application, wherein the catalyst system is composed of an unreacted mixture of a titanium compound component (1) and a phosphorus compound component (2a) or (2b), and is based on transesterification. Before or at the beginning of the reaction, the entire amount of the titanium compound component (1) is added to the reaction system. The reaction is obtained by adding the phosphorus compound component (2a) or (2b) to the transesterification reaction before or at the beginning of the polycondensation reaction. Department. 14 · The manufacturing method according to item 4 of the patent application, wherein the catalyst system is composed of a reaction product of a titanium compound component (1) and a phosphorus compound component (2a), and before or at the beginning of the transesterification reaction The full amount of force was put into the reaction system, and after the transesterification reaction was completed, the reaction mixture was supplied to the polycondensation reaction. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 15. The manufacturing method of item 4 in the scope of patent application, wherein before the vinegar exchange reaction, part of the titanium compound component (1), part of the titanium compound component (1) and phosphorus compound The reaction product of component (2a) or part of the phosphorus compound component (2a) is added to the reaction system, and the remainder is added to the reaction system during or at the end of the transesterification reaction and before or during the polycondensation reaction. in. 1 6. The manufacturing method according to item 2 of the scope of patent application, in which the two paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -72-581777 A8 B8 C8 D8 6. Application scope of patent 6 ( Please read the notes on the back before filling this page.) Before the esterification reaction, add the phosphorus compound component (2a) to the diesterification reaction system, or add a part of the phosphorus compound component (2 a) before the diesterification reaction. Then, the remaining portion is added to the reaction system during or at the end of the diesterification reaction and before or during the polycondensation reaction. 17.—A poly (aromatic ethylene dicarboxylate) resin, characterized in that it is made of a poly (aromatic ethylene dicarboxylate) resin as described in any one of claims 1 to 16 of the scope of patent application. Method maker. i 8. The poly (aromatic ethylene dicarboxylate) resin according to item 17 of the scope of patent application, which further contains 1% by weight or less of amine hindered phenol antioxidant. 19. The manufacturing method according to item 1 of the scope of patent application, wherein the content of antimony element and germanium element contained in the poly (aromatic ethylene dicarboxylate) resin are each controlled to 5/1 000 mol% or less. 20. A polyester fiber, characterized in that it contains a poly (aromatic ethylene dicarboxylate) resin according to any one of claims 17 to 19 of the scope of patent application. 21 The polyester fiber according to item 20 of the patent application scope, in which the main component of the poly (aromatic dicarboxylic acid ethylene glycol) resin is polyethylene terephthalate, printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 22 · A polyester film, characterized in that it contains a poly (aromatic ethylene dicarboxylate) tree as described in any one of claims 17 to 19 in the scope of patent application. 23. As in the scope of patent application, item 22 Polyester film, in which the main component of the poly (aromatic ethylene dicarboxylate) resin is polyethylene terephthalate-73- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 581777 A8 B8 C8 D8 VI. Application scope of patent 7 〇2. A kind of bottle-shaped polyester shaped product, which is characterized by containing poly (aromatic) as described in any one of items 17 to 19 in the scope of patent application. Ethylene dicarboxylate) resin. 25. The bottle-like polyester molded article as claimed in claim 24, wherein the main component of the poly (aromatic dicarboxylic acid) resin is polyethylene terephthalate. ϊ I. —I— ........ j I n (Please read the notes on the back before filling out this page), 11 Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper is printed in accordance with China's national standards (CNS) A4 Specification (210X297 mm) _ 74-Attachment of Patent Year ρ 靑 '· 问範圍)修正本 月20曰 91121795 (以上各棚由本局填柱） 民Question range) Amendment on the 20th of this month 91121795 修正 Α4 C4 581777 翁鋈專利説明書 發明 新型 名稱 發明 創作&gt; 申請人 中 文 製造聚（芳香族二羧酸乙二酯）樹脂之方法，及樹脂製品 英 文 姓 名 國 籍 住、居所 姓 名 (名稱） 國 籍 住、居所 (事務所） PROCESS FOR PRODUCING A POLY(ETHYLENE AROMATIC DICARBOXYLATE ESTER) RESINE, THE RESINE, AND FIBERS, FILMS AND BOTTLE-FORMED PRODUCTS PRODUCED FROM THE RESINE 夫二義 信亮智 延本本 見塚山 (1)(2)(3) (1)日本國愛媛縣松山市北吉田町七七番地 山事業所内 (2)日本國愛媛縣松山市北吉田町七七番地 山事業所内Amend A4 C4 581777 Weng Yi Patent Specification Invention New Name Invention Creation &gt; Applicant's method for making poly (aromatic ethylene dicarboxylate) resin in Chinese, and resin product English name Nationality residence, residence name (name) Nationality residence 、 Home (office) PROCESS FOR PRODUCING A POLY (ETHYLENE AROMATIC DICARBOXYLATE ESTER) RESINE, THE RESINE, AND FIBERS, FILMS AND BOTTLE-FORMED PRODUCTS PRODUCED FROM THE RESINE (3) (1) Inside the Chichichibanchi Mountain Office in Kitakita-cho, Matsuyama City, Ehime Prefecture (2) Inside the Chichichibanchi Mountain Office in Kitakita-cho, Matsuyama City, Ehime Prefecture, Japan 帝人株式会社松 帝人株式会社松 (3)日本國愛媛縣松山市北吉田町七七番地 帝人株式会社 松山事業所内 (1)帝人股份有限公司 帝人株夫会社 (1)日本 ⑴日本國大阪府大阪市中央區南本町一丁目六番七號 代表人 姓 名 (1)長島徹Teijin Co., Ltd.Matsu Teijin Co., Ltd.Matsu (3) Nishichichi, Kitakita-cho, Matsuyama, Ehime Prefecture, Japan Teijin Co., Ltd. (1) Teijin Co., Ltd. Teijin Co., Ltd. (1) Osaka, Japan Representative name (1) Tetsuya Nagashima (21GX 297公釐） 裝 訂 線 581777(21GX 297mm) Gutter 581777 (請先閱讀背面之注意事項再填寫本頁) 進行縮聚合之步驟，其中前述觸媒系爲含有至少1種選自 下述未反應混合物（I)、反應生成物（Π)與未反應生 成物（III)者， 未反應混合物（I )爲 (1 )含有鈦烷氧化物、鈦烷氧化物與芳香族多價羧酸或 其酐之反應生成物群中所選出至少一種之鈦化合物成分， 與（2a)含有下列一般式（1 ): OR2 R'O-C-X—P〈 ( 1 ) II ll'OR3 ’ 0 0 [式（1)中，R^R2及R3各自獨立爲含1至4個碳原子 之烷基；X爲—CH2 —基或下列式（la)所示之基： 一CH一(Please read the precautions on the back before filling this page) The step of polycondensation, in which the catalyst contains at least one selected from the following unreacted mixture (I), reaction product (Π) and unreacted product (III), the unreacted mixture (I) is (1) a titanium compound component containing at least one selected from the reaction product group of a titanium alkoxide, a titanium alkoxide, and an aromatic polyvalent carboxylic acid or an anhydride thereof. , And (2a) contain the following general formula (1): OR2 R'OCX-P <(1) II ll'OR3 '0 0 [In formula (1), R ^ R2 and R3 each independently contain 1 to 4 Carbon atom alkyl group; X is —CH 2 — group or a group represented by the following formula (la): —CH— 經濟部智慧財產局員工消費合作社印製 ]所示至少一種化合物之磷化合物成分的未反應混合物， 前述反應生成物（II)爲 前述鈦化合物成分（1 )與前述磷化合物成分（2a )之反 應生成物， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -68-The unreacted mixture of the phosphorus compound component of at least one compound shown by the Intellectual Property Bureau of the Ministry of Economic Affairs ’s consumer cooperative. The aforementioned reaction product (II) is a reaction between the aforementioned titanium compound component (1) and the aforementioned phosphorus compound component (2a) Product, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -68-
TW91121795A 2001-09-20 2002-09-20 Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin TW581777B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2001286766 2001-09-20
JP2001312387 2001-10-10
JP2001313756 2001-10-11
JP2001362327 2001-11-28
JP2002153571 2002-05-28

Publications (1)

Publication Number Publication Date
TW581777B true TW581777B (en) 2004-04-01

Family

ID=32966785

Family Applications (1)

Application Number Title Priority Date Filing Date
TW91121795A TW581777B (en) 2001-09-20 2002-09-20 Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin

Country Status (1)

Country Link
TW (1) TW581777B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112176453A (en) * 2019-07-03 2021-01-05 江苏家来福纺织有限公司 Four-leaf skin-core structure negative oxygen ion polyester fiber and preparation method thereof
TWI743684B (en) * 2020-02-15 2021-10-21 遠東新世紀股份有限公司 Heat-shrinkable polyester film and its manufacturing method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112176453A (en) * 2019-07-03 2021-01-05 江苏家来福纺织有限公司 Four-leaf skin-core structure negative oxygen ion polyester fiber and preparation method thereof
CN112176453B (en) * 2019-07-03 2021-11-16 江苏家来福纺织有限公司 Four-leaf skin-core structure negative oxygen ion polyester fiber and preparation method thereof
TWI743684B (en) * 2020-02-15 2021-10-21 遠東新世紀股份有限公司 Heat-shrinkable polyester film and its manufacturing method
US11965069B2 (en) 2020-02-15 2024-04-23 Far Eastern New Century Corporation Heat-shrinkable polyester film and method for manufacturing the same

Similar Documents

Publication Publication Date Title
JP4048373B2 (en) Method for producing poly (ethylene aromatic dicarboxylate ester) resin
JP3897756B2 (en) Catalyst for producing polyester and method for producing polyester using the same
TWI385194B (en) Aromatic polyester and its manufacturing method
TW201127871A (en) Process for making polyethylene terephthalate
WO2006064773A1 (en) Polyester resin composition, process for producing the same and molding thereof
JP2003160656A (en) Method of manufacturing polyester and fiber
JP2004067733A (en) Copolyester and its manufacturing method
TWI487727B (en) Method for producing polyester resin
JP2004067924A (en) Polyester, manufacturing process therefor and fiber thereof
JP2000319370A (en) Production of polyester
JP3888884B2 (en) Polyester production method
TW581777B (en) Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin
JP2004091585A (en) Polyethylene terephthalate resin composition and its production method
JP2004175912A (en) Method for producing polyester film
JPH0656975A (en) Polyethylene naphthalate composition and its production
JP2004083737A (en) Polyethylene terephthalate resin composition and method for producing the same
JP2005097466A (en) Polyethylene terephthalate composition, its manufacturing method, and polyethylene terephthalate film
TWI245779B (en) Catalyst for polymerizing polyester, polyester produced by using it and process for producing the polyester
JP2002097263A (en) Production method for polyester
CN116323752A (en) Catalyst particle for polyester production and method for producing polyester using same
JP4669272B2 (en) Method for producing polyethylene terephthalate using bis- (2-hydroxyethyl) terephthalate as a raw material
JP5080096B2 (en) Copolymerized aromatic polyester composition and method for producing the same
JP2004175911A (en) Method for producing polyester film
JP2009167322A (en) Method for producing aromatic polyester
JP4373775B2 (en) Polyethylene naphthalate film

Legal Events

Date Code Title Description
MK4A Expiration of patent term of an invention patent