200521151 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種具有高韌性的聚對苯二甲酸丙 二醇醋（polytrimethylene terephthalate，PTT)樹脂與其製造 方法，該樹脂的數量平均分子量（number average molecular weight，Μη)至少為20,000，且其表示分子量分 散程度的聚合度分佈性指數(polydispersity index，PDI)為 1·3-2·7，以及一種以此樹脂所製得之ρττ纖維。 【先前技術】 專利合作條約W0第99/11709號揭示一種具有 〇·4 2.0 dl/g 極限黏度（intrinsic visc〇sity)的 ρττ 的製造 方法’其係於聚縮合反應（p〇lyc〇n(jensati〇n)中使用填化 合物與金屬化合物作為溶劑。 本發明人對於PTT的製造進行廣泛的研究，結果 PTT #數量平均分子量與聚合度分佈性減(PDI) 對於其品質峰度有更大的影響力。 八一般而s ’依據習知方法而製造的ΡΊΤ之數量平均 义子量為17,0〇〇，且聚合度分佈性指數為2·9。 右使用含數量乎均分子量η，_與聚合度分佈性指 默2·9的ΡΤΤ於制、 3 氣造出的纖維，其抗拉強度(tenacity)低於 g/d’而與製造聚自旨的習知方法相 比，PTT的紡紗效率 200521151 【發明内容】 因此，本發明的目的係提供一種PTT纖維，其抗拉 強度為3.5 g/d或更高且其延伸率（elongation)為20-80% ; 一種用於製造該PTT纖維的PTT樹脂，其數量平均分子 量至少為20,000,且其聚合度分佈性指數(polydispersity index，PDI)為1·3-2·7;以及一種製造該PTT樹脂的方法。 【實施方式】 依據本發明，一種適合製造聚對苯二甲酸丙二醇酯 (polytrimethylene terephthalate，PTT)纖維的 PTT 樹脂，其 物理性質係包含其數量平均分子量至少為20,〇〇〇，以及表 示分子量分佈性的聚合度分佈性指數為1.3-2.7。 當PTT樹脂的數量平均分子量少於2〇,〇〇〇時，該 PTT纖維的抗拉強度明顯地下降，導致較差的纺紗效率。 在這方面，是不可能藉由大幅增快速度而改良紗線(yarn) 的產能。再者，藉由最終製程而使該PTT成為具有所需 性質的纖維紡製品是困難的。 此外，在操作（如編織與針織）中常發生紗線斷裂，而 難以控制PTT纖維的張力，所以會使該ρττ纖維的物理 性質不良地降低。 同樣地，當主要影響PTT樹脂與纖維物理性質的聚 合度分佈性指數高於2.7時，該PTT樹脂中會有高濃度的 低分子量物質，而有不均勻的分子量分佈。因此，會使擠 壓壓力（pack pressure)增加且使擦拭週期(Wiping cycie)降 低，原紗細度(fineness)的不均勻程度會上升，將使得在 200521151 PTT樹脂的紡紗過程中，其生產的原紗(grey yard)的物理 性質變得不一致。 然而，尤以聚合度分佈性指數小於1·3時製造ρττ樹 脂是非常困難的。 依據本發明，係提供一種ΡΤΤ樹脂的製造方法，其 所產生的ΡΤΤ樹脂的數量平均分子量至少為2〇,〇〇〇，以 及其聚合度分佈性指數為1.3-2.7。在這方面，此方法包含 於160_230°C的惰性介質（inert medium)下，處理ΡΤΤ樹脂 57-300個小時，此ρττ樹脂的數量平均分子量為 10,000-18,000且聚合度分佈性指數至少為2·7。此時，該 ΡΤΤ樹脂係依據一熱處理而製造。 基於此點，該ΡΤΤ樹脂於一真空或惰性介質下被處 理，該介質係選自於聯苯烷化物(alkylene diphenyl) (Therm ⑧ S7〇〇 )、氮氣、氬氣(argon gas)、氦氣(helium gas)與氖氣 (neon gas)所組成的群組。 至於氯仿（chloroform)，由於其具有相當低的沸點， 故使用氣仿將難以改良PTT樹脂的數量平均分子量，並 難以降低PTT樹脂的聚合度分佈性指數。 再者，PTT樹脂較佳的處理乃是於i6〇_23〇°C的惰性 介質下，以產生具有良好品質的PTT樹艏。 當在溫度低於160°C處理PTT樹脂時，將無法確保其 數量平均分子量的增加，以及聚合度分佈性指數的下降， 故而無法改良此PTT樹脂的物理性質。另一方面，當在 溫度高於230°C處理PTT樹脂時，此PTT樹脂在熔融後 200521151 會被沉殿出來，從而無法紡紗、射出（inject)或擠壓（extrude) 此PTT樹脂。 同樣地，當處理PTT樹脂的時間少於57個小時，將 無法達成增加數量平均分子量及降低聚合度分佈性指數 的目的，故無法確保該PTT樹脂的物理性質的改良。另 一方面，當處理PTT樹脂的時間超過300個小時，該PTT 樹脂的的數量平均分子量會下降。 此外，藉由PTT樹脂加熱過程，將其保持在下限溫 度為100°C並處理7個小時以上，徹底地自PTT樹脂移除 水份是必要的。 這樣做的理由在於，當其含有水份，而在高於12〇°C 處理PTT樹脂時，其會被水解，將導致該PTT樹脂的變 質（deterioration)。 另外，具有數量平均分子量至少為20,000與聚合度 分佈性指數為1·3_2·7的PTT樹脂，必須依據本發明而用 以製造ΡΤΤ纖維。 參照第一圖，在依據本發明適當地處理ΡΤΤ樹脂後， 分子量較小的ρττ樹脂被轉換為分子量較大的ΡΤΤ樹脂。 再者，依據本發明處理ΡΤΤ樹脂後，ΡΤΤ樹脂的分 子量的分佈會隨ΡΤΤ樹脂分子量的增加而降低。 本發明的ΡΤΤ纖維係利用本發明的ΡΤΤ樹脂而製造 的。此時，該ΡΤΤ纖維的抗拉強度為高於3.5 g/d，且延 伸率為20-80%。 詳細地說’該PTT樹脂以高於3,〇〇〇 m/min的速度進 200521151 行熔紡（melt-spun)，透過延伸製程於50-180°C進行延伸 (draw) ’以及熱固（heat-set)以製造纖維細度為2dpf (dernier per filament，每單絲丹尼）的PTT纖維。 在此方面，該ΡΤΤ樹脂以240-300°C進行熔紡，較佳 的溫度是250-290°C。 當溫度低於240°C，在PTT樹脂的紡紗過程中產生穩 定的熔融樹脂是困難的，該被紡出的PTT纖維具有不佳 的物理性質，且其延伸率不一致。另一方面，當紡紗溫度 咼於 300°C，PTT 纖維的熱變質（thermal decomposition)發 生而引起該PTT纖維紡紗效率的降低。 關於此點，PTT樹脂以3,000-4,000 m/min的速度進 行紡紗，較佳的速度為3,200-3,800 m/min。 當速度低於3,000 m/min時，由於原紗的物理性質會 明顯地隨時間而變，故難以穩定地生產PTT纖維。另一 方面，當速度高於4,000 m/min時，絨毛與紗線常會發生 斷裂，因此，常態性地製造PTT纖維是不可能的。 再者，PTT纖維的第一次延伸溫度為50-90°C，較佳 的溫度為60-80°C。 當第一次延伸溫度低於50°C時，PTT纖維的抗拉強 度與延伸率會降低，且絨毛與妙線斷裂常會發生，因此難 以進行此PTT纖維的延伸。 該理由在於，第一次延伸溫度很低時，會導致構成 PTT纖維的分子鏈的不足。 另一方面，當第一次延伸溫度高於90°C時，難以均 200521151 一地延伸PTT纖維，而使用PPT纖維所製造的原紗之物 理性質的改變過於明顯，以致無法理想地延伸出ΡΤΤ纖 維0 此外，ΡΤΤ纖維的第二次延伸溫度為1〇〇-180。(：，較 佳的溫度為11(M70°C。 當第二次延伸溫度低於100°C時，使用PTT纖維製造 的原紗之物理性質會隨時間而變。另一方面，當第二次延 伸溫度高於180°c時，難以製造物理性質均一的原紗且難 以理想地延伸出PTT纖維。 於本發明中，係依下列方法測得PTT的物理性質： 數量平均分子量與聚合度分佈性指數：PTT的數量 平均與重量平均分子量係由膠體穿透層析（gel permeation chromatography，GPC)裝置所測得，該裝置係 由美商WATERS公司所製造，此係根據聚笨乙烯 (polystyrene)標準方法而測得。此時，是以六氟異丙醇 (hexafluoroisopropanol，HFIP)作為溶劑。 經過一般性地陳述後，可參照以下的實施例而對本 發明得舰-步的理解、然而此處的實施例僅係用以闡 明，而非用以侷限本發明的範圍。 實施例1·3與比較實施·例u 將聚對苯二曱酸丙二醇酯(ΡΤΤ)樹脂3〇〇kg置於體積 為1 m的反應器中，然後依表一所述的條 。 於處理前後，測量該聚對笨二甲酸丙二醇辦^樹脂的 物理性質’該結果如表一中所述。 11 200521151 實施例4 依據實細*例1處理後的PTT以纺伸製程(spin-draw process)製造成原紗。 此時，以預定條件進行紡伸製程，包括使單絲 (monofilament)細度至少為1丹尼（denier)，下限速度為 3,000 m/min，冷卻氣流率為〇·3 m/sec與油性附著度 (adhesiveness)為0·7 wt%。此外，於ρττ進行延伸後， 接著進行熱固。 第一延伸溫度為60-80 °C，且第二延伸溫度為 110-170°C。再者，其所產生的PTT纖維具有（I g/d的 抗拉強度，且其延伸率為31%。 再者，處理前的壓變週期（pack change cycle)為7 天，而在處理後則延長成14天，且於紡紗製程中，紗線 斷裂次數明顯地自每天4次降低成每天1次。 、 PPT纖維係使用32英吋-28針圓形針織器進行圓形針 織製程(circular knitting process)，並於高壓與 11(rc 下 使用藍色2R-SF分散染料(dispersed dye)染色30分鐘，、’ 製造一均勻暗色且觸感柔軟的管狀織布。 12 200521151 表一 ι.2200521151 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a polytrimethylene terephthalate (PTT) resin with high toughness and a method for manufacturing the same, and the number average molecular weight of the resin (number average The molecular weight (Mη) is at least 20,000, and its polydispersity index (PDI), which represents the degree of molecular weight dispersion, is 1.3-2.7, and a ρττ fiber made from this resin. [Prior Art] Patent Cooperation Treaty No. WO 99/11709 discloses a method for manufacturing ρττ with an intrinsic viscosity of 0.4 2.0 dl / g, which is based on a polycondensation reaction (p〇lyc〇n ( Filler compounds and metal compounds are used as solvents in jensati). The present inventors conducted extensive research on the production of PTT. As a result, the PTT # number-average molecular weight and the degree of polymerization degree distribution (PDI) have a greater effect on the quality kurtosis. Influence. The average number of protons produced by s ′ according to the conventional method is 17.00, and the distribution index of the degree of polymerization is 2.9. The degree of polymerization distribution refers to the fibers produced by the PTT produced by Mo 2 · 9, and the gas has a tensile strength (tenacity) lower than g / d '. Compared with the conventional method of producing poly, the PTT Spinning efficiency 200521151 [Abstract] Therefore, the object of the present invention is to provide a PTT fiber having a tensile strength of 3.5 g / d or higher and an elongation of 20-80%; PTT resin of PTT fiber, its number average molecular It is at least 20,000, and its polydispersity index (PDI) is 1 · 3-2 · 7; and a method for manufacturing the PTT resin. [Embodiment] According to the present invention, a polyparaphenylene terephthalate is suitable for manufacturing The physical properties of the PTT resin of polytrimethylene terephthalate (PTT) fibers include a number average molecular weight of at least 20,000, and a polymerization degree distribution index representing the molecular weight distribution of 1.3-2.7. When the PTT resin When the number-average molecular weight is less than 20,000, the tensile strength of the PTT fiber significantly decreases, resulting in poor spinning efficiency. In this regard, it is impossible to improve the yarn by greatly increasing the speed ( yarn). Furthermore, it is difficult to make the PTT into a fiber spinning product with the required properties by the final process. In addition, yarn breakage often occurs in operations (such as weaving and knitting), and it is difficult to control the PTT fiber. Therefore, the physical properties of the ρττ fiber are undesirably reduced. Similarly, when the polymerization degree distribution index of the physical properties of the PTT resin and the fiber is mainly affected At 2.7, the PTT resin will have a high concentration of low molecular weight substances and an uneven molecular weight distribution. Therefore, it will increase the pack pressure and reduce the wiping cycle (Wiping cycie), and the original yarn will be fine. The degree of non-uniformity of fineness will rise, which will make the physical properties of the grey yard produced during the spinning process of 200521151 PTT resin become inconsistent. However, it is very difficult to produce ρττ resin especially when the polymerization degree distribution index is less than 1.3. According to the present invention, a method for manufacturing a PTT resin is provided. The number average molecular weight of the PTT resin produced is at least 20,000, and the polymerization degree distribution index is 1.3-2.7. In this regard, this method involves processing a PTT resin in an inert medium at 160-230 ° C for 57-300 hours. The number average molecular weight of this ρττ resin is 10,000-18,000 and the polymerization degree distribution index is at least 2 · 7. At this time, the PTT resin is manufactured according to a heat treatment. Based on this, the PTT resin is processed in a vacuum or inert medium selected from the group consisting of alkylene diphenyl (Therm ⑧ S700), nitrogen, argon gas, and helium (helium gas) and neon gas (neon gas). As for chloroform, since it has a relatively low boiling point, it is difficult to improve the number-average molecular weight of the PTT resin and reduce the distribution degree index of the polymerization degree of the PTT resin by using a gas-form. Furthermore, the preferred treatment of PTT resin is to produce PTT tree shrews with good quality in an inert medium at 60-20 ° C. When the PTT resin is processed at a temperature lower than 160 ° C, the increase in the number average molecular weight and the decrease in the polymerization degree distribution index cannot be ensured, so the physical properties of the PTT resin cannot be improved. On the other hand, when the PTT resin is processed at a temperature higher than 230 ° C, the PTT resin is melted out in 200521151, which makes it impossible to spin, inject, or extrude the PTT resin. Similarly, when the processing time of the PTT resin is less than 57 hours, the purposes of increasing the number average molecular weight and lowering the polymerization degree distribution index cannot be achieved, so the improvement of the physical properties of the PTT resin cannot be ensured. On the other hand, when the time for processing the PTT resin exceeds 300 hours, the number average molecular weight of the PTT resin decreases. In addition, it is necessary to thoroughly remove water from the PTT resin by heating it at a lower limit temperature of 100 ° C and processing it for more than 7 hours by heating the PTT resin. The reason for this is that when it contains water, when the PTT resin is treated above 120 ° C, it will be hydrolyzed, which will cause the degradation of the PTT resin. In addition, a PTT resin having a number average molecular weight of at least 20,000 and a polymerization degree distribution index of 1 · 3_2 · 7 must be used in accordance with the present invention to produce PTT fibers. Referring to the first figure, after a PTT resin is properly processed according to the present invention, a ρττ resin having a smaller molecular weight is converted into a PTT resin having a larger molecular weight. Furthermore, after processing the PTT resin according to the present invention, the molecular weight distribution of the PTT resin will decrease as the molecular weight of the PTT resin increases. The PTT fiber of the present invention is produced using the PTT resin of the present invention. At this time, the tensile strength of the PTT fiber is higher than 3.5 g / d, and the elongation is 20-80%. In detail, 'The PTT resin was advanced into 200521151 lines of melt-spun at a speed higher than 3,000 m / min, and was drawn at 50-180 ° C through an extension process' and thermoset ( heat-set) to produce a PTT fiber with a fiber fineness of 2 dpf (dernier per filament). In this regard, the PTT resin is melt-spun at 240-300 ° C, and the preferred temperature is 250-290 ° C. When the temperature is lower than 240 ° C, it is difficult to produce a stable molten resin in the spinning process of the PTT resin. The spun PTT fiber has poor physical properties and the elongation is inconsistent. On the other hand, when the spinning temperature is higher than 300 ° C, thermal decomposition of the PTT fiber occurs, causing the spinning efficiency of the PTT fiber to decrease. In this regard, the PTT resin is spun at a speed of 3,000-4,000 m / min, and a preferable speed is 3,200-3,800 m / min. When the speed is lower than 3,000 m / min, it is difficult to stably produce PTT fibers because the physical properties of the raw yarn change significantly with time. On the other hand, when the speed is higher than 4,000 m / min, the fluff and the yarn often break, so it is impossible to normally manufacture the PTT fiber. Furthermore, the first elongation temperature of the PTT fiber is 50-90 ° C, and the preferred temperature is 60-80 ° C. When the first elongation temperature is lower than 50 ° C, the tensile strength and elongation of the PTT fiber will be reduced, and the fluff and the thread breakage will often occur. Therefore, it is difficult to extend the PTT fiber. The reason is that when the first elongation temperature is very low, the molecular chain constituting the PTT fiber becomes insufficient. On the other hand, when the first elongation temperature is higher than 90 ° C, it is difficult to uniformly extend the PTT fiber in 200521151, and the physical properties of the raw yarn produced using the PPT fiber are changed so significantly that the PTT cannot be extended ideally. Fiber 0 In addition, the second elongation temperature of the PTT fiber is 100-180. (: The preferred temperature is 11 (M70 ° C.) When the second elongation temperature is lower than 100 ° C, the physical properties of the raw yarn made from PTT fiber will change with time. On the other hand, when the second When the secondary elongation temperature is higher than 180 ° c, it is difficult to produce a raw yarn with uniform physical properties and it is difficult to ideally extend the PTT fiber. In the present invention, the physical properties of PTT are measured according to the following methods: Number average molecular weight and degree of polymerization distribution Property index: The number average and weight average molecular weight of PTT are measured by gel permeation chromatography (GPC) device, which is manufactured by American company WATERS. This device is based on polystyrene standard. Measured by the method. At this time, hexafluoroisopropanol (HFIP) is used as the solvent. After a general statement, the following examples can be used to understand the ship-to-step understanding of the present invention. The examples are only for clarification, and are not intended to limit the scope of the present invention. Example 1.3 and Comparative Examples · Example u Put 300 kg of polytrimethylene terephthalate (PTT) resin in a volume of 1 m reactor, then according to the strip described in Table 1. Before and after the treatment, the physical properties of the poly (p-phenylene terephthalate) resin were measured. The results are as described in Table 1. 11 200521151 Example 4 Fine * Example 1 The processed PTT is made into a raw yarn by a spin-draw process. At this time, the spinning and drawing process is performed under predetermined conditions, including making the monofilament fineness of at least 1 denier. ), The lower limit speed is 3,000 m / min, the cooling airflow rate is 0.3 m / sec, and the oily adhesion is 0.7 wt%. In addition, after stretching at ρττ, it is then thermosetted. First extension The temperature is 60-80 ° C, and the second elongation temperature is 110-170 ° C. Moreover, the PTT fiber produced has a tensile strength of (I g / d, and its elongation is 31%. Further The pack change cycle before processing was 7 days, and after processing it was extended to 14 days. In the spinning process, the number of yarn breaks was significantly reduced from 4 times per day to 1 per day. PPT fiber is a circular knitting proce ss), and dyed with blue 2R-SF dispersed dye under high pressure and 11 (rc for 30 minutes, ’to produce a uniform dark-colored and soft-touch tubular woven fabric. 12 200521151 Table 1 ι.2
1處理前Μη : PTT樹脂處理^ 2處理前PDI:PTT樹脂處理前的聚合度分佈性指數 3溫度：PTT樹脂的處理溫度（t) θ 4染色時間：FIT樹脂處理過程 ' U〇C下將其所含水份移除時， 該PTT樹月旨染色時間（小時） 5處理時間：PTT樹脂的總處理時間(小時） 6處理後Μη:ρττ樹脂處理後的數量平均分子量 7處理後PDI:PTT樹脂處理後的聚合度分佈性^數 曰由上述說明可知，本發明係提供- PTT樹脂，其數 里平均/刀子置至少^ 20,000,且其聚合度分佈性指數為 1·3-2·7。此PTT樹脂的優點在於其有均勻的分子量分佈， 如此可於ρττ纖維的紡紗製程，降低擠壓壓力（pack 13 200521151 pressure)的增加，並延長壓變週期(packchangecyci勾與擦 拭週期(wiping CyCie)。藉此，增加Ρττ纖維的產能，增加 利用ΡΤΤ纖維製造原紗的-致性關，且改善原紗的物 理性質。 進一步，在ΡΤΤ纖維的紡紗製程中，原紗斷裂減少， 增加ΡΤΤ纖維的產能。 再者，依據本發明的ΡΤΤ纖維有其優點，在於該ΡΤΤ 纖維的較大分子量可導致相當高的抗拉強度，故Ρττ纖 維原有且所希望得到的物理性質，例如柔軔性、彈性恢復 力、柔軟度與抗化學性於後續製程(如假撚紗製程、延伸 製程、針織製程與紡紗製程）中幾乎不會降低。此外，在 後續製程中，ΡΤΤ纖維的可加工性被改善了，而且，不論 ρττ纖維的用途為何，如衣料或工業用纖維，ρττ纖維的 製造成本均被降低。 同樣地，依據本發明的ΡΤΤ纖維可有效地應用於製 造射出及擠壓產物。 本發明已於上述中加以說明，須理解的是所使用的用 詞是做為性質的說明，而非用以限制本發明的範圍。依照 本發明的教示而做出許多的變化與修飾是可能的。因此， 須瞭解的是，本發明之保護範圍應視所附之申請專利範圍 所界定者為準，而非僅限於說明書中特別的陳述。 14 200521151 【圖式簡單說明】 第一圖係表示本發明使用膠體穿透層析（gel permeation chromatography，GPC)裝置分析聚對苯二甲 酸丙二醇S旨樹脂的分析圖譜。 【主要元件符號說明】 無1 Mη before treatment: PTT resin treatment ^ 2 PDI before treatment: Polymerization degree distribution index before PTT resin treatment 3 Temperature: PTT resin treatment temperature (t) θ 4 Dyeing time: FIT resin treatment process When the moisture is removed, the PTT tree dyeing time (hours) 5 processing time: the total processing time of the PTT resin (hours) 6 after treatment Mn: ρττ resin treated average molecular weight 7 after treatment PDI: Distribution degree of polymerization degree after PTT resin treatment ^ According to the above description, the present invention provides-PTT resin, which has an average / knife setting of at least ^ 20,000, and a polymerization degree distribution index of 1 · 3-2 · 7. The advantage of this PTT resin is that it has a uniform molecular weight distribution, so it can reduce the increase of squeeze pressure (pack 13 200521151 pressure) in the spinning process of ρττ fiber, and extend the compression change cycle (packchangecyci hook and wiping cycle (wiping CyCie ). In this way, increase the production capacity of Pττ fiber, increase the consistency of using PTT fiber to produce raw yarn, and improve the physical properties of the raw yarn. Further, in the spinning process of PTT fiber, the raw yarn breakage is reduced, increasing PTT The capacity of the fiber. Furthermore, the PTT fiber according to the present invention has its advantages in that the larger molecular weight of the PTT fiber can lead to a relatively high tensile strength, so the physical properties of the original and desired Pττ fiber, such as flexibility In the subsequent processes (such as false twist yarn process, extension process, knitting process and spinning process), the flexibility, elastic resilience, softness and chemical resistance will hardly be reduced. In addition, in the subsequent process, the processing of PTT fiber The properties are improved, and regardless of the use of ρττ fibers, such as clothing or industrial fibers, the cost of manufacturing ρττ fibers is Lower. Similarly, the PTT fiber according to the present invention can be effectively applied to the production of injection and extrusion products. The present invention has been described above. It should be understood that the terminology used is used as a description of properties, rather than It is used to limit the scope of the present invention. Many changes and modifications are possible in accordance with the teachings of the present invention. Therefore, it must be understood that the scope of protection of the present invention shall be determined by the scope of the attached patent application. 14 200521151 [Schematic description] The first diagram shows that the present invention uses a gel permeation chromatography (GPC) device to analyze polytrimethylene terephthalate S resin [Analysis map of the main components.]
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