200302300 A7 B7 五、發明説明（1 ) (發明所屬之技術領域） 本發明係關於適合供製造工業用如輪胎簾布、強力輸 送帶等有多層塡充空間的穩定聚酯紗線之連續生產方法。 多層塡充空間的聚酯紗線特別是供針織之用，作爲X 業產品的加強成份，如輸送帶、V字帶等。高模數、低收 縮及高抗疲勞都是這些多層穩定聚酯紗線所必須符合的要 求。 高抗疲勞紗的固有黏度必須大於〇.83dl/g。 所需要的高分子大都是由凝結而成，故呈固體狀態。 這製程通常是由織物黏度約〇.6dl/g的高分子開始。凝結 後的片必須經融熔後再旋轉成絲。這通常是用壓出成型機 製作。‘ 多層穩定聚酯紗線一般是經兩種不同的旋轉及抽絲程 序所生產。這兩種程序係以2000m/min以上的速度開始。 其不同點在於：用2階段作法，先將旋轉抽絲所得的紗捲 繞起來’然後分別以50Om/min的速度抽絲。适1段程序 ，又稱爲高速旋轉抽絲程序。此後，抽絲及捲絲係在7〇〇〇 m/min下進行的。 (先前技術） 這些程序各有其優缺點： 例如美國專利US4，195,052號說明一生產改良的聚酯 細絲方法。依據此一文獻，該法使用的旋轉速度在500到 3000m/min之間。但沒有說明其效果如何，以及破裂的細 絲數目多少。也沒有在紡織突起下使用加熱器。這不可避 ^^尺度適用中國國家標準(CNS ) A4規格（210'/ 297公瘦1 • J 衣-- C請先閲讀背面之注意事項再填寫本頁) *訂 經濟部智慧財產局員工消費合作社印製 200302300 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（2 ) 免的會導致一核心鞘結構出現，並使旋轉抽絲細絲的結晶 度增加。因而會影響其抽取可能性不足。最後，低產率及 高破裂細絲數量等缺點都會無法避免的一一展現。 歐洲專利EP0799331B1說明一工業用細絲紗的生產方 法，使用於紗線的捲繞速度爲6000m/min以上。其法爲 將凝結成固體的片其黏度爲〉0 · 86dl/g ’溶解在一壓力成型 機裏，然後送入旋轉抽絲裝置。 此種凝結成固體的作法，缺點是將會導致片的黏度不 均勻。例如，一平均黏度爲〇.98dl/g的片，其外表面的黏 度會大於1.2dl/g。 壓力成型高黏度所需要的溫，度約300°C。這樣高溫會 相對的導致高黏度退化，至〇.〇6dl/g或以上，視旋轉位置 數目以及在輸送線上與旋轉抽絲系統中熔漿的滯留時間而 定。 黏度退化程度與旋轉抽絲細絲中的羧基數量的增加有 關。羧基濃度增加與黏度減退增加，對於一個熟悉此方面 技藝者而言，則是量測熔漿穩定度的依據，此因熱穩定度 改變會導致旋轉抽絲破裂尾端的增加及增加細絲的破裂量 。在多層穩定聚酯紗線裏，其羧基增加將會使紗在進一步 加工處理時影響其熱及水解之穩定度。 歐洲專利EP0526740B1說明一種方法，能控制旋轉抽 絲細紗的雙折射率與結晶度之比率。這是透過操作以脂族 雙羧酸來修改聚乙烯對酸，其中有5到10個碳原子及/或 環狀羧酸，其碳醯鍵是有角度的，或者是其環狀核心帶具 (請先閱讀背面之注意事項再填寫本頁)200302300 A7 B7 V. Description of the invention (1) (Technical field to which the invention belongs) The present invention relates to a continuous production method for stable polyester yarns with multiple layers of filling space suitable for manufacturing industries such as tire cords and high-power transmission belts. Multi-layered polyester yarns for filling space are especially used for knitting, as a reinforcing component of X industry products, such as conveyor belts, V-belts, etc. High modulus, low shrinkage, and high fatigue resistance are all requirements that these multilayer stable polyester yarns must meet. The inherent viscosity of high fatigue resistance yarn must be greater than 0.83dl / g. Most of the required polymers are made by coagulation, so they are in a solid state. This process usually starts with a polymer with a fabric viscosity of about 0.6 dl / g. The coagulated sheet must be fused and then rotated into filaments. This is usually made with an extruder. ‘Multi-layer stabilized polyester yarns are generally produced by two different spinning and spinning processes. These two programs are started at speeds above 2000 m / min. The difference lies in that the two-stage method is used to first wind up the yarn roll obtained by spinning and spinning, and then each of the yarns is drawn at a speed of 50 Om / min. Suitable for 1 segment program, also known as high-speed spinning wire drawing program. Thereafter, the drawing and winding were performed at 7000 m / min. (Prior art) These procedures each have their advantages and disadvantages: for example, U.S. Patent No. 4,195,052 describes a method for producing improved polyester filaments. According to this document, the method uses a rotation speed between 500 and 3000 m / min. It did not say how effective it was or how many filaments were broken. No heater is used under the textile protrusions. This unavoidable ^^ standard applies to China National Standard (CNS) A4 specifications (210 '/ 297 male thin 1 • J clothing-C Please read the precautions on the back before filling this page) * Order the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 200302300 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) It will lead to the emergence of a core sheath structure and increase the crystallinity of the spinning filaments. Therefore, it will affect its insufficient extraction possibility. Finally, disadvantages such as low productivity and high number of broken filaments are inevitable. European patent EP0799331B1 describes a method for producing industrial filament yarns, which is used for yarn winding speeds of 6000 m / min or more. The method is to dissolve a solidified tablet with a viscosity of> 0 · 86 dl / g ′, dissolve it in a pressure forming machine, and then send it to a rotary wire drawing device. This method of coagulating into a solid has the disadvantage that it will lead to uneven viscosity of the tablet. For example, for a tablet with an average viscosity of 0.98 dl / g, the viscosity of the outer surface will be greater than 1.2 dl / g. The temperature required for pressure forming high viscosity is about 300 ° C. This high temperature will relatively lead to high viscosity degradation, up to 0.06 dl / g or more, depending on the number of rotation positions and the residence time of the melt on the conveyor line and the spinning wire drawing system. The degree of viscosity degradation is related to the increase in the number of carboxyl groups in the spinning filaments. The increase in the carboxyl group concentration and the decrease in viscosity are a basis for measuring the stability of the melt for a person skilled in this field. This change in thermal stability will lead to an increase in the end of the spinneret and increase the breakage of the filament. the amount. In multilayer stabilized polyester yarns, the increase in carboxyl groups will affect the thermal and hydrolytic stability of the yarn during further processing. European patent EP0526740B1 describes a method capable of controlling the ratio of the birefringence and the crystallinity of the spinning spinning yarn. This is the modification of polyethylene to acid by manipulation of aliphatic dicarboxylic acids, which has 5 to 10 carbon atoms and / or cyclic carboxylic acids, whose carbon 醯 bonds are angled, or whose cyclic core bands have (Please read the notes on the back before filling this page)
C 訂 Μ 本紙張尺度適用中國國家標準（CNS )A4规格（210X 297公釐） 200302300 A7 B7 五、發明説明（ 有修改的替代物及/或經過使用含有3到1〇個碳原子的烷 烴或雙環炔、2或3乙醇或聚乙二醇來修改。 這一程序的缺點是後凝結的聚乙烯對酸無法在市場上 取得。而是經特別化學上修改過的聚乙烯對酸。這種經化 學修改的聚乙烯對酸係是在凝結成固體狀態下後，接著再 壓力成型成高黏度的片。且在這過程中，會同時開始增加 高黏度退化及提高羧基數。再者缺少羧基的正確數量資料 與缺少生產的工業紗的終端模數資料，均與後來的處理有 關聯，也會影響空間穩定紗的性能。 歐洲專利EP(M23213說明一生產聚乙烯對酸紗的方法 。這紗的高終端模數在2〇g/den以上。其羧基穩定度差’ 其相對的低.破裂強度及空間穩定度（E4.5 + HAS 177 °C <13.5% )特別是缺少製程的性能資料（生產量、破裂細 絲數量）足以證明其生產效果不彰。 雖然我們已知有一系列生產多層塡充穩定的聚酯紗線 的方法存在，但一直留有需要改良的空間。即更少的破裂 尾端數以及更大工業規模的細紗生產方法。 (發明內容） 因此本發明旨在提供一製程··其生產的紗線要有均勻 一致的良好機械材質，能特別適合作爲車胎、輸送帶及V 帶的加強材料，並能使用在市場上可以取得的聚乙烯片’ 以促進多層穩定紗線的產量及減少其破裂細絲量。 是故，本發明進一步的目的是提供一種方法，其中： -能使用市場上可以即時取得的，僅具織物黏度的聚乙 (請先閱讀背面之注意事項再填寫本頁) 訂—*-- i#. 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（CM)A4規格（210X 297公釐） 200302300 A7 B7 五、發明説明（4 ) 烯對酸片作爲原料。 -應用熔漿後凝結程序來提高黏度。 -使高黏度熔漿有高均勻性。 -在熔漿後凝結時會使聚乙烯對酸濃度趨於穩定。 -在旋轉抽絲作業裏，會有一個低黏度退化或低數量增 加的聚乙烯對酸結果出現。 -能使聚乙烯對酸的細絲能設定在一最佳的結構狀態。 -能使紗線呈現一特別好的及均勻的物理材質，特別是 在LASE5模數、熱收縮及終端模數方面。 -低破裂細紗數量。 (實施方法） 達成生產供工業用多層聚酯紗線這個目的之方法爲： 一將聚乙烯對酸片，其固有黏度在0.55到0.70dl/g之間 ，其增減變化小於〇.〇2dl/g，與羧基濃度減少媒劑一 倂加入一壓力成型機來熔融及混合。 -然後將熔漿送至反應器來處理這高黏度的熔漿，其中 熔漿經後凝結程序至其固有黏度大於〇.9dl/g。其羧 基濃度降至小於15mmol/kg。反應器裏的溫度在268 到278t之間。C Order M This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 200302300 A7 B7 5. Description of the invention (with modified alternatives and / or through the use of alkanes containing 3 to 10 carbon atoms or Modified by bicycloalkyne, 2 or 3 ethanol, or polyethylene glycol. The disadvantage of this procedure is that post-condensed polyethylene versus acid is not available on the market. Instead, it is specifically chemically modified by polyethylene versus acid. The chemically modified polyethylene is acidified after it is coagulated into a solid state, and then pressure-molded into a high-viscosity sheet. In the process, it will begin to increase high-viscosity degradation and increase the number of carboxyl groups. Furthermore, it lacks carboxyl The correct quantity data and the lack of terminal modulus data of the industrial yarn produced are related to subsequent processing and will also affect the performance of the space-stable yarn. European patent EP (M23213 describes a method for producing polyethylene acid yarn. The high terminal modulus of the yarn is above 20g / den. Its carboxyl group stability is poor, and its relative low. Rupture strength and space stability (E4.5 + HAS 177 ° C < 13.5%), especially the lack of process performance Material (production volume, number of broken filaments) is sufficient to prove that its production effect is not good. Although we know that there are a series of methods to produce multi-layer filled and stable polyester yarn, there is always room for improvement. The number of broken ends and the production method of spun yarns on a larger industrial scale. (Invention) Therefore, the present invention aims to provide a process ... The yarn produced by it must have a uniform and good mechanical material, which can be particularly suitable for car tires and transportation Reinforcement materials for belts and V-belts, and polyethylene sheets that are available on the market can be used to promote the production of multilayer stable yarns and reduce the amount of broken filaments. Therefore, a further object of the present invention is to provide a method, Among them:-Polyethylene with fabric viscosity that can be obtained on the market in real time (please read the precautions on the back before filling this page) Order — *-i #. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies the Chinese National Standard (CM) A4 specification (210X 297 mm) 200302300 A7 B7 V. Description of the invention (4) Ethylene-to-acid tablets as raw materials. Post-coagulation process to increase viscosity.-Make high viscosity melts have high homogeneity.-Make the polyethylene concentration to stabilize acid when it coagulates after melting.-In the spinning operation, there will be a low viscosity degradation. Or a low amount of polyethylene against acid results.-Can make polyethylene to acid filaments can be set in an optimal structural state.-Can make the yarn present a particularly good and uniform physical material, especially In terms of LASE5 modulus, heat shrinkage, and terminal modulus.-Low number of spun yarns. (Implementation method) The method to achieve the purpose of producing multilayer polyester yarns for industrial use is as follows:-Polyethylene to acid sheet, its inherent viscosity Between 0.55 and 0.70 dl / g, the increase or decrease is less than 0.02 dl / g, and the carboxyl group concentration reducing agent is added to a pressure forming machine to melt and mix. -The melt is then sent to a reactor to process this highly viscous melt, where the melt is subjected to a post-coagulation procedure until its inherent viscosity is greater than 0.9 dl / g. Its carboxyl group concentration was reduced to less than 15 mmol / kg. The temperature in the reactor was between 268 and 278 t.
-強使在反應器裏處理之熔漿，經過旋轉抽絲的鑄模孔 ，在鑄模孔牆的剪力大於每秒2300。然後進入一系 列的熱處理區、冷卻區以及調節區，俾使固化的紗線 得以完成旋轉抽絲工作，然後使用一取出裝置在旋轉 抽絲取出速度V爲2500到3400m/min下取出（TAKE 本紙悵尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) C'-Forcing the molten slurry processed in the reactor through the spinning hole of the mold, the shear force on the wall of the mold hole is greater than 2300 per second. Then enter a series of heat treatment zone, cooling zone and adjustment zone, so that the solidified yarn can complete the spinning and spinning work, and then use a take-out device to take out at a spinning speed of 2500 to 3400m / min怅 Applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) C '
、1T 經濟部智慧財產局員工消費合作社印製 200302300 A7 B7 五、發明説明（5 ) -OFF)。所得到的旋轉抽絲細紗其結構特性Q能滿足 以下的條件： (請先閱讀背面之注意事項再填寫本頁) - 1.333 xlO"3 X V+8.03<=Q <= -1.333 xlO3 xV+9.03 其中Q是商數，是由旋轉抽絲細絲的雙折射率及結晶 度相除後乘以1000倍而成。這結構化的旋轉抽絲細 絲係經兩個抽絲區抽取，至其總抽取比例到達在1.7/1 及2·6/1之間，再經熱設定，然後放鬆，並在捲繞速度 大於5500m/min下捲繞之。 依據本發明的方法其優點說明在申請專利範圍第2至 第5項。 本發明還提供一抽取聚乙烯對酸多層細絲，如申請專 利範圍第6項所載，申請專利範圍第7項至第9項亦具有 本發明所生產的抽取聚乙烯對酸多層細絲的優點。 此外，本發明也提供使用本發明的多層聚酯紗線來加 強工業產品性能，特別是車胎、輸送帶及V帶及類似產品。 經濟部智慧財產局員工消费合作社印製 依據本發明，其方法的起始點爲市場上可取得的聚乙 烯對酸片，其織物黏度在0.55到0.70dl/g之間。這些片的 黏度變化通常在加減〇.〇2dl/g之間。這些聚乙烯對酸片在 壓力成型機中熔融。在壓力成型機入口處再以量計加入羧 基降低媒劑，並在壓力成型機裏與PET熔漿均勻混合。由 壓力成型機出來的熔漿溫度必須低於275°C，最好是低於 272°C。 其後，要使用一個熔漿幫浦，最好是齒輪幫浦，將熔 漿計量送入反應器。熔漿在反應器中，俟其凝結到黏度 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 200302300 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（6 ) 0.90dl/g以上，同時還要將pet熔漿的羧基濃調整到低於 1 5mmol/kg 〇 用來處理高黏度熔漿的反應器可以是任何一種反應器 ，能確保好的混合以及均勻的溫度，而且，尤其是凝結的 聚合物不得在其中任何地區沈澱，包括反應器壁、攪拌器 內等等。在德國DE3743051A1有說明一個合適的反應器， 本申請說明內也很明白的將其納入參考資料。 高黏度聚酯熔漿的羧基濃度是經有效設定的，使用碳 酸亞烴酯以及溴化烯丙三苯基膦，最好是自4000到16000 ppm，依聚酯而定。在德國DE19526405A1所說的一個合適 程序，在本申請說明內也很明白的將其納入參考資料。 反應器內的反應溫度最好是在攝氏268到278之間。 使用真空來設定反應器中最後的黏度。真空，就是壓力’ 最好是定在0.3到1.2mbar之間。最後黏度的變化範圍在 加減0.0075dl/g之間。 在反應器中凝結的熔漿此後是用幫浦打到輸送線再到 個別的抽絲管，其中裝有抽絲幫浦。 在輸送線中的熔漿溫度是保持在低於攝氏285 °此溫 度係明顯地低於高黏度PET片擠壓成型抽絲機所能達到的 溫度，超過攝氏295。依據目前的發明，在此製程抽絲系 統輸送線中黏度的降低是低於0.06dl/g。如此’比傳統的 擠壓成型抽絲機少一半。 抽絲幫浦，最好是單獨加熱的，將熔漿壓入鑄模。鑄 模包含過濾物，最好是非針織的金屬過濾物，這時所有的 ---------·$------------A (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） 200302300 A7 _ ___ B7___ 五、發明説明（7 ) 雜物都可由熔漿中除去。鑄模的壓力最好是在200到600 bar之間，而且是能依據熔漿的流量調節的。 熔漿是在抽絲溫度攝氏300到315時擠壓通過紡織突 起的鑄模孔。孔的直徑與數量的選擇得使在鑄模通道中的 剪切速率在每秒2500到7500範圍內，其計算方法如下列 方程式： r =4F/;r 3 其中F是通過毛細孔的流量（m3/s)，r是毛細孔的直徑 (m)。 紡織突起的出口面立即接上一熱處理區，有100到 500mm長，溫度爲攝氏270到370。用來抑止熔漿的固化 。緊接著熱處理區是冷卻區，有150到700mm長，最好 是用放射狀冷卻軸。原則上也可以使用橫向冷卻軸。 紗的冷卻係使用10到40m3空氣/聚合物kg。冷卻空 氣的溫度最好是在攝氏15到40之間。緊接在冷卻區之後的 是調節區，在這裡紗停留在50到150 χ10_3秒。 調節區內壁的溫度是低於60°C。離開調節區後，所形 成的細絲即告紡絲完成，並以抽絲速度2500到3400m/min 取出之。其後細絲由4個二重機器的兩個抽出區抽出，其 後用熱設定及放鬆，以及用超過5500m/min的速度捲繞。 很驚奇的是，抽絲操作，只有在以下Q値條件下，才 能滿意的生產高尺寸穩定度的紗： -1.333 xlO'3 xV+8.03<=Q<= -1.333 xl03xV+9.03 其中 2500 m/min <= V <=3400m/min。 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ~ (請先閱讀背面之注意事項再填寫本頁) ，裝 訂 經濟部智慧財產局員工消費合作社印焚 200302300 A7 B7 五、發明説明（8 ) 在此，Q是商數，是由1000倍雙折射率與由第一二 重機抽出的絲其結晶度量測而得。v是旋轉抽絲取出速度 ，與第一二重機的表面速度相同。 一個在此種技藝上具有一般技術的人都能經由調整下 開條件來設定Q値到預定的範圍如：旋轉抽絲溫度、鑄模 孔直徑、熱處理區長度及溫度、冷卻空氣的流量/速度及 溫度、調節區的滯留時間。基本上，高的Q値會導致或增 進可抽絲性，譬如高生產量與少斷裂的機率。在旋轉抽絲 的纖維中如結晶度高即會增加抽絲困難。但是也是要使抽 出的紗具有所需要的高尺寸穩定度的先決條件。 另外，聚合物黏度變化範圍<=+/-0.0075dl/g，是高效 能的先決條件。. ' 所獲得的多絲聚酯絲會展現以下物理與化學綜合的物 性以及製程成效： (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 黏度 羧基 破裂強度 尺寸穩定度DS 終端係數 每l〇km的斷裂細絲 每t的斷裂端 <: <: 0.84 dl/g 21 mmol/kg 60 cN/tex 10 cN/tex DS=LaSe5/HLS，溫度攝氏 160 160cN/tex 7 8 依據本發明所生產的紗線能用來作輪鲐、輸送帶及v 皮帶等增強材料。 本紙張尺度適用中國國家標準（CNS) M規格（21〇>< 297公| ) 200302300 A7 B7 五、發明説明（9 ) 下開例子以及以上說明中的材料性質數據是由以下的 程式得之： 黏度是由〇.5g聚酯在lml，3:2 (重量比）的酚/1，2二 氯苯溶液中，其溫度爲攝氏25。 羧基濃度是由光度滴定決定，此係用0.05N乙醇氫氧 化鉀溶液，對聚乙烯對酸與正甲酚/氯仿溶液70 : 30 (重 量比）中的溴百里藍而決定者。 旋轉抽絲而得的細絲，其雙折射率是由極化顯微鏡決 定。此極化顯微鏡有一傾斜補整器、及用楔形切割之綠色 過濾器（540mm )。量測的是當線性極化的光通過細絲時 ’按一般光線及特別光線的差距計算而定。雙折射率則是 ' 路徑差異及細絲直徑所得之商。在旋轉抽絲操作中抽絲的 纖維即自取出機制下移除。 未經抽絲纖維的結晶度是由纖維的密度決定。密度係 由一裝滿正庾烷/四氯化碳的梯度管在攝氏23溫度時決定 。梯度管的準備及校正是依據ASTMD1505-68專利案的 記載。 其後，結晶度計算如下列程式所示： ds— da X 100 K (%)-- dc — da ds—樣品的量測密度（g/ccm) 如一1〇〇%無定形相的理論密度（1.335§/(^111) dc—l〇〇%結晶相的理論密度（ 1.529g/ccm) 強度性質是由對紗施加50轉/m的扭動而決定者，其 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 200302300 A7 B7 V. Description of Invention (5) -OFF). The structure characteristic Q of the obtained spinning spinning yarn can meet the following conditions: (Please read the precautions on the back before filling this page)-1.333 xlO " 3 X V + 8.03 < = Q < = -1.333 xlO3 xV +9.03 where Q is the quotient, which is obtained by dividing the birefringence and crystallinity of the spinning filaments and multiplying by 1000 times. This structured spinning wire is drawn through two wire drawing areas, until the total drawing ratio reaches between 1.7 / 1 and 2. · 6/1, and then it is set by heat, then relaxed, and at the winding speed It is wound at more than 5500m / min. The advantages of the method according to the invention are described in claims 2 to 5 of the scope of the patent application. The present invention also provides a polyethylene-acid multilayer filament for extraction, as described in item 6 of the scope of patent application, and items 7 to 9 of the patent scope also have advantage. In addition, the present invention also provides the use of the multilayer polyester yarn of the present invention to enhance the performance of industrial products, particularly car tires, conveyor belts and V-belts and the like. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the present invention, the starting point of the method is a commercially available polyethylene-to-acid tablet with a fabric viscosity of 0.55 to 0.70 dl / g. The viscosity of these tablets usually varies between plus and minus 0.02 dl / g. These polyethylene / acid sheets were melted in a compression molding machine. A carboxyl reducing agent is added at the inlet of the pressure forming machine in an amount, and it is evenly mixed with the PET melt in the pressure forming machine. The temperature of the melt from the press must be below 275 ° C, preferably below 272 ° C. Thereafter, a slurry pump, preferably a gear pump, is used to meter the slurry into the reactor. The melt is in the reactor, and its condensation to viscosity. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 200302300 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) Above 0.90dl / g, at the same time, the carboxyl concentration of the pet melt must be adjusted to less than 15mmol / kg. The reactor used to process the high viscosity melt can be any kind of reactor, which can ensure good mixing and uniformity. The temperature, and especially the coagulated polymer, must not settle in any of these areas, including reactor walls, agitators, etc. A suitable reactor is described in German DE3743051A1, which is also clearly incorporated into the reference in the description of this application. The carboxyl group concentration of high viscosity polyester melts is effectively set, using alkylene carbonate and brominated allyltriphenylphosphine, preferably from 4000 to 16000 ppm, depending on the polyester. A suitable procedure described in German DE19526405A1 is also clearly incorporated into the reference material in the description of this application. The reaction temperature in the reactor is preferably between 268 and 278 ° C. A vacuum was used to set the final viscosity in the reactor. The vacuum, that is, the pressure, is preferably set between 0.3 and 1.2 mbar. The final viscosity varies between 0.0075 dl / g. The melt condensed in the reactor is then hit by a pump to the conveyor line and to individual wire drawing tubes, which are equipped with wire drawing pumps. The temperature of the slurry in the conveying line is kept below 285 ° C. This temperature is significantly lower than the temperature that can be achieved by high-viscosity PET sheet extrusion and drawing machines, and exceeds 295 ° C. According to the current invention, the viscosity reduction in the conveyor line of this process spinning system is less than 0.06 dl / g. In this way, it's half less than a conventional extrusion wire drawing machine. The drawing pump, preferably heated separately, presses the melt into the mold. The mold contains a filter, preferably a non-knit metal filter. At this time, all --------- $$ -------- A (please read the precautions on the back first) (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 200302300 A7 _ ___ B7___ 5. Description of the invention (7) Debris can be removed from the slurry. The pressure of the mold is preferably between 200 and 600 bar, and it can be adjusted according to the flow of the melt. The melt is extruded through the mold holes at the spinning temperature of 300 to 315 ° C. The diameter and number of holes are selected so that the shear rate in the mold channel is in the range of 2500 to 7500 per second. The calculation method is as follows: r = 4F /; r 3 where F is the flow rate through the pores (m3 / s), r is the diameter (m) of the pores. The exit surface of the textile protrusion is immediately connected to a heat treatment zone, which is 100 to 500 mm long and has a temperature of 270 to 370 degrees Celsius. Used to inhibit the solidification of the melt. The heat treatment zone is followed by a cooling zone, which is 150 to 700 mm long, preferably with a radial cooling shaft. In principle, transverse cooling shafts can also be used. The yarn cooling system uses 10 to 40 m3 of air / polymer kg. The temperature of the cooling air is preferably between 15 and 40 degrees Celsius. Immediately after the cooling zone is the conditioning zone, where the yarn stays at 50 to 150 x 10_3 seconds. The temperature of the inner wall of the conditioning zone is below 60 ° C. After leaving the adjustment zone, the formed filaments are finished spinning and taken out at a spinning speed of 2500 to 3400 m / min. The filaments are then withdrawn from the two extraction zones of the four double machines, after which they are set and relaxed with heat, and wound at a speed in excess of 5500 m / min. It is very surprising that the yarn drawing operation can only satisfactorily produce yarn with high dimensional stability under the following Q 値 conditions: -1.333 xlO'3 xV + 8.03 < = Q < = -1.333 xl03xV + 9.03 of which 2500 m / min < = V < = 3400m / min. The scale of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) ~ (Please read the precautions on the back before filling out this page), binding to the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Co-printing, 200302300 A7 B7 V. Invention Explanation (8) Here, Q is a quotient, which is measured from the double refractive index of 1000 times and the crystal metric of the silk drawn by the first double machine. v is the speed of taking out the spinning wire, which is the same as the surface speed of the first double machine. A person with ordinary skills in this skill can set the Q 値 to a predetermined range by adjusting the opening conditions such as: spinning temperature, mold hole diameter, heat treatment zone length and temperature, cooling air flow / speed and Temperature, residence time in the adjustment zone. Basically, high Q 値 will cause or increase drawability, such as high throughput and less chance of breakage. If the crystallinity is high in the spin-drawn fiber, it will increase the difficulty of drawing. But it is also a prerequisite for the drawn yarn to have the required high dimensional stability. In addition, the range of polymer viscosity < = + /-0.0075dl / g is a prerequisite for high performance. . 'The obtained multifilament polyester yarn will show the following physical and chemical properties and process results: (Please read the notes on the back before filling this page) Breaking strength, dimensional stability, DS, terminal coefficient, breaking end per t of broken filaments at 10 km <: <: 0.84 dl / g 21 mmol / kg 60 cN / tex 10 cN / tex DS = LaSe5 / HLS, temperature 160 Celsius / 160 cN / tex 7 8 The yarn produced according to the present invention can be used as reinforcement materials such as wheel reels, conveyor belts, and v-belts. This paper size applies the Chinese National Standard (CNS) M specification (21〇 < 297g |) 200302300 A7 B7 V. Description of the invention (9) The example below and the material property data in the above description are obtained from the following formula No .: Viscosity is 0.5g polyester in lml, 3: 2 (weight ratio) phenol / 1,2 dichlorobenzene solution, the temperature is 25 ° C. The carboxyl group concentration is determined by photometric titration. It is determined by using 0.05N ethanol potassium hydroxide solution, polyethylene para-acid and n-cresol / chloroform solution 70:30 (weight ratio) bromine thyme. The birefringence of the filament obtained by spinning is determined by a polarization microscope. This polarization microscope has a tilt trimmer and a green filter (540mm) cut with a wedge. What is measured is that when linearly polarized light passes through the filament, it is determined as the difference between general light and special light. Birefringence is the quotient of the path difference and the filament diameter. The fiber drawn during the spin-draw operation is removed by the take-out mechanism. The crystallinity of the unspun fiber is determined by the density of the fiber. The density is determined by a gradient tube filled with n-hexane / carbon tetrachloride at a temperature of 23 ° C. The preparation and calibration of the gradient tube is based on the records of the ASTMD1505-68 patent. Thereafter, the crystallinity is calculated as shown in the following formula: ds— da X 100 K (%)-dc — da ds—the measured density (g / ccm) of the sample is a theoretical density of 100% amorphous phase ( 1.335§ / (^ 111) dc—100% Theoretical density of crystalline phase (1.529g / ccm) The strength property is determined by applying a twist of 50 revolutions / m to the yarn. The paper size is applicable to Chinese national standards (CNS) Λ4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印紫 200302300 A7 B7 五、發明説明（10) 長度爲250mm，伸長率爲2〇〇mm/min。於力與延伸中的 力相等於5%時，除以線性密度，所得的力稱爲Lase5。 終端率是於力與申展四線中達2.4%由斷裂強度與斷 裂伸展，並要除以0.024後的差異計算出來的。 熱空氣收縮（HAS)係依美國Testrite的收縮測試計 測定者。其採用的溫度爲攝氏160，須穿透0.05cN/dtes， 處理時間爲4分鐘。 (實施方式） 本發明再用下列的範例來說明： 比較範例1至3 PETP 片，黏度 0.98dl/g、COOH 終端群 16mmol/kg、 含水量爲25ppm，經熔解在德國Bannag公司的7E型擠 壓成型機內。聚合物熔液再經以160bar壓力通過靜態混 合器入40cm3的熔漿計量幫浦。旋轉抽絲幫浦輸送熔漿， 溫度控制在攝氏298，至ZimmerBN52旋轉抽絲系統內， 其特徵有一長方形紡織突起裝置還有內有一不同的紡織突 起孔的幾何形狀。對300細絲，其熔漿流量是設定在最後 終端密度爲llOOdtex。鑄模壓力是300bai*。旋轉抽絲的多 絲紗係用一交叉的冷卻系統冷卻。抽絲完成時再用紗加油 機在室溫下引到第一三角二重機。這第一二重機的速度在 定義上與旋轉抽絲取出速度相同。旋轉抽絲的紗則被引到 這第一二重機之下游，到一捲繞裝置，由提供的樣品來決 定其雙折射率及結晶度。要生產尺寸穩定的紗線’紗要由 這第一二重機引到超過3個更多的加熱的三角二重機，再 (請先閱讀背面之注意事項再填寫本頁) 訂 I# 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（210X 297公釐） 200302300 A7 B7 五、發明説明（Η ) (請先閱讀背面之注意事項再填寫本頁), 1T Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Yinzi 200302300 A7 B7 V. Description of the invention (10) The length is 250mm and the elongation is 2000mm / min. When the force and the force in the extension are equal to 5%, divide the linear density and the resulting force is called Case5. The termination rate is calculated from the difference between the tensile strength and the fracture elongation of 2.4% in the fourth line of Yuli and Shenzhan, which is divided by 0.024. Hot air shrinkage (HAS) is measured according to the American Testrite shrinkage tester. Its temperature is 160 ° C, it must penetrate 0.05cN / dtes, and the processing time is 4 minutes. (Embodiment) The present invention is further illustrated by the following examples: Comparative Examples 1 to 3 PETP tablets, viscosity 0.98 dl / g, COOH terminal group 16 mmol / kg, water content 25 ppm, melted in Germany, the 7E type extrusion by Bannag company Inside the press. The polymer melt was passed through a static mixer at a pressure of 160 bar into a 40 cm3 melt metering pump. Rotary spinning pump conveys the melt, the temperature is controlled at 298 degrees Celsius, and the ZimmerBN52 spinning spinning system is characterized by a rectangular textile protrusion device and a different geometry of textile protrusion holes. For 300 filaments, the melt flow rate is set at a final terminal density of llOOdtex. The mold pressure is 300bai *. The spinning multifilament yarns are cooled by an intersecting cooling system. When the drawing is completed, the yarn dispenser is used to lead to the first triangle duplex machine at room temperature. The speed of this first double machine is the same as the speed of taking out the spinning wire. The spinning yarn is led downstream of this first double machine to a winding device, and the birefringence and crystallinity are determined by the sample provided. To produce dimensionally stable yarns, the yarn has to be led from this first double machine to more than three more heated triangular double machines, and then (please read the precautions on the back before filling this page) Order I # 经济 部 智慧The paper size printed by the Property Cooperative Consumer Cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 200302300 A7 B7 V. Description of the invention (Η) (Please read the precautions on the back before filling this page)
捲繞。在第一與第三二重機之間，紗會經過二段抽絲，同 時在第三二重機上，紗即被熱設定。在第三二重機與捲繞 機之間，紗得以放鬆。這三個加熱的二重機其溫度如下： 二重機 2 : 85°C 二重機 3 : 240°C 二重機 4 : 150°C 在每一組，二重機4與二重機3的放鬆比例都是 0.995。其他的設定則顯示在表中。這三個範例的旋轉抽 絲操作的製程參數都是一樣。 發明範例4一 6 其下列規格的PETP片： / 黏度.0.60dl/g COOH 終端群 22mmol/kg 含鍊量310ppm 含憐量12ppm 含水量 27ppm 經濟部智慧財產局員工消費合作社印災 被放在Barmag公司的7E10型擠壓成型機熔解，其熔 液經4〇CCm的計量幫浦，在溫度攝氏271下被送到高黏 度自行淸潔聚合物凝結反應器（HVSR)，詳如德國專利 DE3743051A1 的說明。 羧基濃度係以6000ppm的碳酸乙二醇與溴化烯丙三 苯基膦混合物（混合比：1〇〇:8)，在75°C下由齒輪幫浦 送至壓縮成型機的入口設定之。 在高黏度自動淸潔反應器凝結的溫度是272°C，其真 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 200302300 Λ7 B7 五、發明説明（12 ) 空壓力爲0.8mbar、滯留時間爲160分鐘。該高度凝結的 熔發被打出反應器後被送至旋轉抽絲幫浦。在輸送線的壓 力差是135bai·。在輸送線的反應器與旋轉抽絲幫浦之間 的滯留時間是12分鐘。在輸送線中裝有兩個靜態混和器。 這條線是用Diphyl加熱到280°C。 旋轉抽絲幫浦輸送熔漿到ZimmerBNllO型旋轉抽絲 系統，其中有一圓形的紡織突起裝置以及一環形的紡織突 起。熔漿流量是設定在最後線性密（dtex )。旋轉抽絲的 多絲紗用一放射性冷卻系統由外部及內部冷卻。抽絲完成 時再用紗加油機在室溫下引到一三角二重機。紡織突起與 紗加油機之間的距離爲4250mm。這第一二重機的速度在 定義上與旋轉抽絲取出速度相同。旋轉抽絲的紗則被引到 這第一二重機的下游，到一捲繞裝置，提供樣品來決定雙 折射率及結晶度。要生產空間穩定的紗線，紗由這第一二 重機引到超過3個更多加熱的三角二重機，再捲繞。在第 一與第三二重機之間，紗會經過抽絲，在第三二重機上時 ，紗會被熱設定。在第三二重機與捲繞機之間，紗可以放 鬆。這三個加熱的二重機的溫度如下·· 二重機 2 : 85t：Coiled. Between the first and third double machines, the yarn will be drawn through two sections, and at the same time, the yarn will be hot set on the third double machine. Between the third double machine and the winder, the yarn is relaxed. The temperature of the three heated duplexers is as follows: Duplex 2: 85 ° C Duplex 3: 240 ° C Duplex 4: 150 ° C In each group, the relaxation ratios of Duplex 4 and Duplex 3 are 0.995. . The other settings are shown in the table. The process parameters for the three spinning spin operations are the same. Invention Example 4-6 PETP tablets with the following specifications: / Viscosity. 0.60dl / g COOH Terminal Group 22mmol / kg Chain Content 310ppm Mercury Content 12ppm Moisture Content 27ppm Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on Barmag The company's 7E10 extrusion molding machine melted, and its melt was sent to a high-viscosity self-cleaning polymer coagulation reactor (HVSR) at a temperature of 271 degrees Celsius through a metering pump of 40CCm, as described in German Patent DE3743051A1. Instructions. The carboxyl group concentration was set at 6000 ppm of a mixture of ethylene carbonate and bromoallyltriphenylphosphine (mixing ratio: 100: 8), which was sent from the gear pump to the inlet of the compression molding machine at 75 ° C. The condensation temperature in the high-viscosity automatic cleaning reactor is 272 ° C. The actual paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) 200302300 Λ7 B7 V. Description of the invention (12) The air pressure is 0.8 mbar, retention time is 160 minutes. This highly condensed melt is driven out of the reactor and sent to a rotary spinning pump. The pressure difference on the conveyor line is 135bai ·. The residence time between the reactor of the transfer line and the spinning spinning pump is 12 minutes. Two static mixers are installed in the conveyor line. This line was heated to 280 ° C with Diphyl. The rotary spinning pump conveys the melt to the ZimmerBNllO rotary spinning system, which has a circular textile protrusion device and an annular textile protrusion. The melt flow is set at the final linear density (dtex). Spinning multifilament yarns are cooled externally and internally with a radioactive cooling system. When the drawing is completed, the yarn dispenser is used to lead to a triangular double machine at room temperature. The distance between the textile protrusions and the yarn dispenser was 4250 mm. The speed of this first double machine is the same as the speed of taking out the spinning wire. The spinning yarn is led downstream of this first double machine to a winding device to provide samples to determine the birefringence and crystallinity. To produce space-stable yarns, the yarn is led from this first double machine to more than three more heated triangle double machines and then wound. Between the first and third double machines, the yarn will be drawn. When on the third double machine, the yarn will be hot set. The yarn can be loosened between the third double machine and the winder. The temperatures of the three heated double machines are as follows: · Double machine 2: 85t:
二重機 3 : 240°C 二重機 4 ·· 140°C 在每一組，二重機4與二重機3的放鬆比例都是 0.995。其他的設定則顯示在下列表中。這三個範例的旋 轉抽絲操作的製程參數都是一樣。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） J ^t.-- (請先閲讀背面之注意事項再填寫本頁) 訂 i# 經濟部智慧財產局員工消費合作社印災 200302300 經濟部智慧財產局員工消f合作社印製 A7 B7 五、發明説明（13) 表 樣品號碼 1 2 3 4 5 6 發明 發明 發明 PERT 原料，IV dl/dg 0.98 0.98 0.98 0.6 0.6 0.6 壓縮成型機旋轉抽絲沒有HVSR 是 是 是 否 否 否 直接用HVSR旋轉抽絲 否 否 否 是 是 是 HVSR後之IV dl/dg 0.94 0.94 0.94 HVSR後之COOH群 mmol/g 14 14 14 旋轉抽絲溫度 °C 310 310 310 310 310 310 後熱器溫度 °C 330 330 330 330 330 330 長方形紡織突起及橫切冷卻 °c 是 是 是 否 否 否 冷卻空氣溫度 °c 16 16 16 20 20 20 冷卻軸長度 mm 300 300 300 冷卻速度 m/sec 0.6 0.6 0.6 環狀型紡織突起及放射狀冷卻 否 否 否 是 是 是 冷卻空氣流量 Nm3kg/PETP 28 28 28 冷卻軸長度 mm 1500 1500 1500 在調節區的滯留時間 msec 無 Μ 無 72 60 54 旋轉抽絲的取出速度 m/min 2500 3000 3250 2500 3000 3250 Q 3.8 3.1 3 5.1 4.8 4.2 第一次抽絲 1: 1.6 1.45 1.3 1.6 1.45 1.3 總抽絲 1: 2.45 2.1 L9 2.45 2.1 1.95 總放鬆比例 1: 0.974 0.976 0.985 0.975 0.977 0.982 捲繞速度 m/min 5965 6150 6080 5970 6155 6220 紗黏度 dl/g 0.86 0.86 0.86 0.88 0.88 0.88 IV dl/g 紗的COOH群 mmol/kg 26 26 25 20 19 15 破裂強度 cN/tex 70.5 69 65 71.6 70.5 70.2 空間穩定度 cN/tex% 9.4 10.3 12.1 10.3 11.3 13.2 收縮攝氏160 % 3.5 3.4 2.9 3.4 3.1 2.6 LASE5 cN/tex 33 35 35 35 35 37 終端係數 cN/tex 230 247 274 106 115 132 破裂端/t n 8 10 11 5 6 6 破裂細絲 n/10 km 10 14 21 3 5 6 (請先閲讀背面之注意事項再填寫本頁) Q = ΙΟΟΟχ雙折射率/結晶度 尺寸穩定度= Lase5/在攝氏160的收縮 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐）Duplex 3: 240 ° C Duplex 4 · 140 ° C In each group, the relaxation ratio of Duplex 4 and Duplex 3 is 0.995. The other settings are displayed in the table below. The process parameters of the spinning and drawing operations for all three examples are the same. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) J ^ t .-- (Please read the precautions on the back before filling this page) Order i # Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative, India 200302300 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 Cooperative cooperatives V. Invention description (13) Table sample number 1 2 3 4 5 6 Invention invention Invention PERT raw material, IV dl / dg 0.98 0.98 0.98 0.6 0.6 0.6 Compression molding machine rotation Spinning without HVSR Is it possible to directly spin the filament with HVSR? No No Yes IV IV after HVSR dl / dg 0.94 0.94 0.94 COOH group after HVSR mmol / g 14 14 14 Spinning temperature ° C 310 310 310 310 310 310 Rear heater temperature ° C 330 330 330 330 330 330 Rectangular textile protrusions and cross-section cooling ° c Yes No No Cooling air temperature ° c 16 16 16 20 20 20 Cooling shaft length mm 300 300 300 Cooling speed m / sec 0.6 0.6 0.6 Circular textile protrusion and radial cooling No No No Yes Yes Cooling air flow rate Nm3kg / PETP 28 28 28 Cooling shaft length mm 1500 1500 1500 Dwell time in the adjustment zone msec No M No 72 60 54 Take-out speed of rotary wire drawing m / min 2500 3000 3250 2500 3000 3250 Q 3.8 3.1 3 5.1 4.8 4.2 First wire drawing 1: 1.6 1.45 1.3 1.6 1.45 1.3 Total draw Silk 1: 2.45 2.1 L9 2.45 2.1 1.95 Total relaxation ratio 1: 0.974 0.976 0.985 0.975 0.977 0.982 Winding speed m / min 5965 6150 6080 5970 6155 6220 Yarn viscosity dl / g 0.86 0.86 0.86 0.88 0.88 0.88 IV dl / g COOH of yarn Group mmol / kg 26 26 25 20 19 15 Rupture strength cN / tex 70.5 69 65 71.6 70.5 70.2 Space stability cN / tex% 9.4 10.3 12.1 10.3 11.3 13.2 Shrinkage 160 ° C 3.5 3.4 2.9 3.4 3.1 2.6 LASE5 cN / tex 33 35 35 35 35 37 Terminal coefficient cN / tex 230 247 274 106 115 132 Rupture end / tn 8 10 11 5 6 6 Rupture filament n / 10 km 10 14 21 3 5 6 (Please read the precautions on the back before filling this page ) Q = ΙΟΟΟχ birefringence / crystallinity dimensional stability = Lase5 / shrinkage at 160 Celsius This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm)