(i) (i)200304510 玖、發明說明 (發明說明應敘明··發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 本發明係有關於一種製造聚丙烯單纖維絲之方法，該聚 丙蟑單纖維絲在230°C /2.16公斤下之熔體流動指數（melt fl〇w index，MFI)為2至16克/10分並擁有大於0.050毫米之直徑及 改進之耐磨損性；本發明亦係有關於此種聚丙烯之單纖維 絲及其用途。 二維度聚丙晞紡織物品作為化學、製藥及食品工業過爐 用之耐化學及機械過瀘構件，是非常令人關注的事。在此 一領域中，最特別需要的，是擁有直徑大於0.050毫米之相 當粗單纖維絲。 純聚丙晞單纖維絲有形成大量粉塵之缺點，因為此一物 質在編織過程時耐磨損性很低。磨損的問題在其他熱塑性 塑膠之情形也有所知。因此，ΕΡ-Α2-0 784 107號提及聚醯 胺、聚酯或聚丙晞之熔紡單纖維絲，該等纖維絲預定用於 造紙機之成形織品及切邊機之絲線。根據該專利，耐磨損 單纖維絲係利用70至99重量％之成纖（fiber-forming)聚合物 及1至30重量％之經馬來酸酐改質之聚乙晞/聚丙烯橡膠， 及其他添加劑而製得。然而，就成纖聚合物而言，實例僅 限於聚醯胺尼龍6及聚對苯二酸乙二醇酯，以及pA_6, 6/pA_6 共聚龜胺。旋紡速度並未詳細說明。 由EP-A-1 059 370號也得知一種製造預定用於紡織用途之 聚丙烯早纖維絲之方法。該方法使用金屬茂催化之等規聚 丙缔作為原料，右想達到所要收縮率特徵，則該聚丙缔之 熔體流動指數必須大於19克/1〇分。這是因為要獲得低收縮 (2) 200304510 發明說明續頁 率，MFI值必須要高。 n 以上專利描述了 10 dpf(每纖絲旦 數）[0.03953毫米]之佘入&上 王疋向紗（fully oriented yarn，FOY)， 及2 dpf [〇·〇1768亳米]之部 僅提出一般性的指標。並 份定向紗。就所製造之紗而言 無單纖維絲之說明。 本發明之問題包括提 之經濟方法。本發明之 進耐磨損性之粗聚丙缔 供一種製造粗耐磨聚丙烯單纖維絲 另一問題包括製造在編織時具有改 單纖維絲。 又一問題係 高性能物品， 用途。 包括&供擁有良好耐磨性、可供製造二維度 尤Jt 曰猫 、 /、疋t、疋用於過瀘之物品之粗單纖維絲之 這些問題都根據本發明將20至〇 〇1重量％之添加劑加至 擠壓機之聚丙婦上游，將熔體紡入水浴中，將其拉製成單 纖維絲及將單纖維絲捲繞而獲得解、、夫。 作為聚丙烯，較佳係使用擁有熔體流動指數大於2克/1〇 分，較佳6至13克/10分，特別是I]至η克/10分之均聚物。 MFI大於16克/10分時，有產生不足機械性質及低劣财磨損 性之缺點。 適當的是使用由潤滑劑、填料及熱穩定劑之組合所組成 之添加劑。作為潤滑劑、填料及熱穩定劑之組合，〇_5至L2 重量％聚乙婦蜡、碳酸1弓及位阻酚已註明特別適合。 在另一具體中，很適當的是使用〇 〇5至1〇重量。/〇，尤其 是0.3至1.0重量％之潤滑劑作為添加劑。作為潤滑劑，特別 適當的是羧酸之金屬鹽、直鏈或支鏈煙類、氟彈性體及聚 二甲基矽氧烷。 200304510 (3) 雜然_、頁 在又一具體中，很適當的是使用填料作為添加劑。作為 添加劑，0.01至0.1重量％之珍膠（aerosil)及0.1至1.0重量％之 後酸#5已t正明特別適合。 在又一具體中，很適當的是使用0.1至0.8重量％之熱穩定劑 作為添加劑。位阻酚、亞磷酸鹽及膦酸鹽已証明特別適合。 在又一具體中，很適當的是使用1至20重量％擁有熔點^ 140°C之-聚丙諦/聚乙烯作為添加劑。 很適當的是，就對應於最大抗張應力之伸長率（斷裂伸 長率）低於35%，較佳低於30%時，單纖維絲擁有強度至少50 cN/德士。這是因為強度低於50 cn/德士時，線紗有在編織 過程時增加斷裂次數的缺點。 也很重要的是，單纖維絲之磨損必須低於0.05%。這是 因為當磨損大於0.05%時，會在編織時發生不規則性，這 疋由於雜（reed)太快結垢所致。此意謂清潔作業之間隔必 須縮短，因而降低織機（loom)之生產力。 很適當的是’單纖維絲在120°C下經處理24小後，尤其 & &丨共彳目老化後必須具有相對斷裂能〉丨〇〇%之特徵。這有 ^ ^遽、器壽命之優點，當其承受相當高之熱應力及侵襲性 化學物時。 才良^本發明之單纖維絲特別適合於製造預定供化學、製 藥及食品工業過瀘用之二維度物品。 本發明現將藉助實力更詳細說明。 聚合物 作為成纖聚合物，試驗中使用5種不同市售聚丙烯，這 200304510 (4) 些在230°C /2.16公斤下之熔體流動指數自6.0至13.0克/10分 不等。每次使用100公斤桶及偏心混合機，將50公斤聚丙 烯粒摻混。摻混係視添加劑而定使用二種不同方法進行。 各種不同方法都將在實例中說明。將粒子/添加劑摻混物 直接加入擠壓機並溶解。 旋紡條件： 擠壓機：直徑：40毫米；圓筒長度：L/D = 25 擠壓機壓力：80巴 產出量：19.76公斤/時 5加熱區； 旋纺泵：排氣容積（swept volume) : 10立方釐米/轉； 旋紡元件：電加熱； 計量系：23.19 rpm 模： 直徑：0.7毫米 毛細管長度：3 X D 水浴： 模/水洛距離：45毫米 溫度：30°C 拉製階段及加熱溝道 拉製階段1 : 7支輥；輥直徑：230毫米；1加熱溝道 拉製階段2 : 7支輥；輥直徑：230毫米；1加熱溝道 拉製階段3 : 7支輥；輥直徑：230毫米；2加熱溝道 拉製階段4 : 4支輥；輥直徑：230毫米。 旋纺製劑： 5%含水溶液。 200304510 (5) 試樣製備： 實例2、5、6及7 : 在細粉添加劑，如填料、潤滑劑、熱穩定劑等等之情形 時’製程係由在黏著劑如BAYSIL0N M 100(I) (Bayer公司商 標）中將粒子滾動半小時而開始，然後將其餘添加劑加入 並再摻混1.5小時。 貫例4 : 在改質聚烯烴之情形時，將由聚丙埽及絲pp/PE改質之 聚烯烴所組成、具熔點〉14〇它之粒子之摻混物摻混丨小時。 表1列示諸實例。 表1 實例 添加劑 直徑 [mm] 強度 [cN/tex] 斷裂伸長 率[%] 比斷裂能 [cN.cm/ dtex] 機械常數 [cN/tex] 線密度均 勻度[U%] 烘箱老化 時之相對 斷裂能24 h/no0^ 磨損[%] 〜1 0 0.159 55.6 18.4 0.349 238.5 2.43 77.3 0.1717 2 0.15/0,3/0.35 0.160 57.7 19.3 0.373 253.5 1.66 183.6 0.0156 3 0 0.160 54.7 19.1 0.354 239.1 76.2 0.5543 4 ---- 10 0.159 51.1 19.1 0.329 223.3 1.82 180.2 0.0254 5 0.5 0.160 54.8 17.9 0.334 231.8 2.60 69.0 0.017 6 0.15/0.15 0.159 55.3 18.2 0.344 235.9 2.16 68.3 0.018 7 ____ 0.15/0.3,0.35 0.159 55.6 18.6 0.356 239.8 2.31 71.0 8 0 0.160 54.3 19.1 0.35 237.1 1.94 139.8 0.0128 _9 0 0.160 56.3 19.4 0.37 248.0 1.67 ________ 103.3 0.0386(i) (i) 200304510 发明, description of the invention (the description of the invention should be stated ... the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings are briefly explained) The present invention relates to a method for manufacturing polypropylene monofilament yarn Method, the melt flow index (MFI) of the polypropylene monofilament filament at 230 ° C / 2.16 kg is 2 to 16 g / 10 minutes and has a diameter greater than 0.050 mm and improved resistance Abrasion resistance; the present invention also relates to the monofilament yarns of such polypropylene and uses thereof. Two-dimensional polypropylene textile articles are of great concern as chemically and mechanically resistant components used in chemical, pharmaceutical, and food industry furnaces. In this area, what is most particularly needed is to have a relatively thick monofilament filament with a diameter greater than 0.050 mm. Pure polypropylene single-filament yarn has the disadvantage of forming a large amount of dust, because this material has very low abrasion resistance during the weaving process. The problem of wear is also known in the case of other thermoplastics. Therefore, EP-A2-0 784 107 refers to melt-spun monofilament yarns of polyamide, polyester, or polypropylene, which are intended for use in forming fabrics for paper machines and yarns for trimming machines. According to the patent, abrasion-resistant monofilament yarns use 70 to 99% by weight of a fiber-forming polymer and 1 to 30% by weight of maleic anhydride-modified polyethylene / polypropylene rubber, and And other additives. However, as far as the fiber-forming polymer is concerned, examples are limited to polyamido nylon 6 and polyethylene terephthalate, and pA_6, 6 / pA_6 co-monamine. The spinning speed is not specified. EP-A-1 059 370 also discloses a method for producing polypropylene early fiber yarns intended for textile applications. This method uses metallocene-catalyzed isotactic polypropylene as a raw material. To achieve the desired shrinkage characteristics, the melt flow index of the polypropylene must be greater than 19 g / 10 minutes. This is because to obtain a low shrinkage (2) 200304510 Invention Description Continuation Rate, the MFI value must be high. The above patents describe the insertion of 10 dpf (denier per fiber) [0.03953 mm] & fully oriented yarn (FOY), and the 2 dpf [〇 · 〇1768 亳 米] part only Propose general indicators. Orientation yarn. In the case of manufactured yarns, there is no description of monofilament yarns. Problems with the present invention include economic methods. The rough polypropylene of the present invention provides abrasion-resistant polypropylene monofilament yarns. Another problem includes the manufacture of monofilament yarns that have modified fibers during weaving. Another problem is high-performance items, uses. These problems include & thick monofilament yarns that have good abrasion resistance and can be used to make two-dimensional cats, cats, /, 疋 t, and 疋 for passing articles. According to the present invention, 20 to 001 The additive in weight% is added upstream of the polypropylene of the extruder, the melt is spun into a water bath, and it is drawn into single fiber filaments and the single fiber filaments are wound to obtain a solution. As the polypropylene, a homopolymer having a melt flow index of more than 2 g / 10 minutes, preferably 6 to 13 g / 10 minutes, particularly 1] to η g / 10 minutes is preferably used. When the MFI is more than 16 g / 10 minutes, there are disadvantages that insufficient mechanical properties and poor abrasion properties are generated. It is appropriate to use an additive composed of a combination of a lubricant, a filler and a heat stabilizer. As a combination of lubricants, fillers and thermal stabilizers, 0-5 to L2 weight percent polyethenyl wax, carbonic acid 1 bow and sterically hindered phenols have been indicated as being particularly suitable. In another embodiment, it is appropriate to use from 0.05 to 10 weight. / 〇, especially 0.3 to 1.0% by weight of a lubricant as an additive. As the lubricant, particularly suitable are metal salts of carboxylic acids, linear or branched cigarettes, fluoroelastomers, and polydimethylsiloxane. 200304510 (3) Miscellaneous _, page In another specific example, it is appropriate to use a filler as an additive. As additives, 0.01 to 0.1% by weight of aerosil and 0.1 to 1.0% by weight of acid # 5 have been particularly suitable. In yet another embodiment, it is appropriate to use a thermal stabilizer in an amount of 0.1 to 0.8% by weight as an additive. Hindered phenols, phosphites and phosphonates have proven to be particularly suitable. In yet another embodiment, it is suitable to use 1 to 20% by weight of polypropylene-polyethylene / polyethylene having a melting point ^ 140 ° C as an additive. It is quite appropriate that when the elongation (elongation at break) corresponding to the maximum tensile stress is less than 35%, preferably less than 30%, the monofilament yarn has a strength of at least 50 cN / taxi. This is because yarns with a strength below 50 cn / taxi have the disadvantage of increasing the number of breaks during the weaving process. It is also important that the abrasion of the monofilament yarn must be less than 0.05%. This is because when the abrasion is more than 0.05%, irregularities occur during weaving, which is caused by reed scaling too quickly. This means that the interval between cleaning operations must be shortened, thereby reducing the productivity of the loom. It is very suitable that the 'single-fiber yarns' have a characteristic of relative breaking energy> 丨 00% after aging at 120 ° C for 24 hours, especially after aging by the & & This has the advantages of ^ ^ 遽, device life, when it is subjected to relatively high thermal stress and aggressive chemicals. Cailiang ^ The single-fiber yarn of the present invention is particularly suitable for manufacturing two-dimensional articles intended for chemical, pharmaceutical, and food industry applications. The invention will now be explained in more detail by virtue of its strength. Polymers As fiber-forming polymers, five different commercially available polypropylenes were used in the tests. These 200304510 (4) have a melt flow index at 230 ° C / 2.16 kg ranging from 6.0 to 13.0 g / 10 minutes. Use 100 kg barrels and an eccentric mixer to blend 50 kg of polypropylene pellets. Blending is performed using two different methods depending on the additives. Various methods are explained in the examples. Add the particle / additive blend directly to the extruder and dissolve. Spinning conditions: extruder: diameter: 40 mm; cylinder length: L / D = 25 extruder pressure: 80 bar output: 19.76 kg / hour 5 heating zone; spinning pump: exhaust volume (swept volume): 10 cubic centimeters / revolution; spinning element: electric heating; metering system: 23.19 rpm mold: diameter: 0.7 mm capillary length: 3 XD water bath: mold / water distance: 45 mm temperature: 30 ° C drawing stage And heating channel drawing stage 1: 7 rolls; roll diameter: 230 mm; 1 heating channel drawing stage 2: 7 rolls; roll diameter: 230 mm; 1 heating channel drawing stage 3: 7 rolls ; Roll diameter: 230 mm; 2 heating channel drawing stage 4: 4 rolls; roll diameter: 230 mm. Spin spinning preparation: 5% aqueous solution. 200304510 (5) Sample preparation: Examples 2, 5, 6, and 7: In the case of fine powder additives such as fillers, lubricants, heat stabilizers, etc., the process is based on adhesives such as BAYSILON M 100 (I) (Bayer's trademark), rolling the particles for half an hour to begin, then adding the remaining additives and blending for another 1.5 hours. Example 4: In the case of modified polyolefin, a blend of particles consisting of polypropylene and silk pp / PE modified polyolefin, having a melting point of> 14 °, is blended for one hour. Table 1 lists examples. Table 1 Example Additive diameter [mm] Strength [cN / tex] Elongation at break [%] Specific energy at break [cN.cm/dtex] Mechanical constant [cN / tex] Linear density uniformity [U%] Relative to oven aging Breaking energy 24 h / no0 ^ Wear [%] ~ 1 0 0.159 55.6 18.4 0.349 238.5 2.43 77.3 0.1717 2 0.15 / 0, 3 / 0.35 0.160 57.7 19.3 0.373 253.5 1.66 183.6 0.0156 3 0 0.160 54.7 19.1 0.354 239.1 76.2 0.5543 4- -10 0.159 51.1 19.1 0.329 223.3 1.82 180.2 0.0254 5 0.5 0.160 54.8 17.9 0.334 231.8 2.60 69.0 0.017 6 0.15 / 0.15 0.159 55.3 18.2 0.344 235.9 2.16 68.3 0.018 7 ____ 0.15 / 0.3, 0.35 0.159 55.6 18.6 0.356 239.8 2.31 71.0 8 0 0.160 54.3 19.1 0.35 237.1 1.94 139.8 0.0128 _9 0 0.160 56.3 19.4 0.37 248.0 1.67 ________ 103.3 0.0386
*斷裂能為最初值之百分比； 實例1 ··(對照實例1):具13.0克/10分MFI之聚丙烯； 實例2 ··具6.0克/1〇分MFI之聚丙烯，以組合物為添加劑’ 實例3 :(對照實例2) ··具12.0克/1〇分MFI之聚丙烯； -10- 200304510 發明說明續頁 實例4:具12.0克/1〇分MFI之聚丙婦，以熔點>140°C之PP/PE 為添加劑； 實例5 :具13.0克/1〇分MFI之聚丙烯，以潤滑劑為添加劑； 實例6 :具13.0克/1〇分MFI之聚丙烯，以熱穩定劑基之組合 物為添加劑； 實例7:具13.0克/1〇分MFI之聚丙婦，以組合物為添加劑； 實例8 :、具13.0克/1〇分MFI之聚丙烯，具抗氣體褪色穩定； 實例9 :具9.0克/1〇分MFI之聚丙晞，具抗氣體褪色穩定。 為能更詳細說明，結果均以圖表及圖片顯示。 這些顯TF : • 圖1為一直方圖，顯示根據實例2加與不加添加劑之 比斷裂能、烘箱老化及磨損； -圖2係根據實例4加與不加添加劑之比斷裂能、烘箱 老化及磨損行為； 圖3a為根據實例1 (對照實例），不加添加劑以所製造 碼數為函數之磨損行為；及 -圖3b為根據實例8 (具體實例），加添加劑並以所製造 碼數為函數之磨損彳于為。 在圖1中，左邊的一對方拄代表比斷裂能，中間的為烘 損，根據實例2加及不加添加劑。左 箱老化及右邊的為磨損 側方枯反#* Break energy is a percentage of the initial value; Example 1 (Comparative Example 1): polypropylene with 13.0 g / 10 min MFI; Example 2 · polypropylene with 6.0 g / 10 min MFI, with the composition as Additives' Example 3: (Comparative Example 2) ·· Polypropylene with 12.0 g / 10 MFI; -10- 200304510 Description of the Invention Continued Example 4: Polypropylene with 12.0 g / 10 MFI, with melting point & gt 140 ° C PP / PE as additive; Example 5: Polypropylene with 13.0 g / 10 minutes MFI, with lubricant as additive; Example 6: Polypropylene with 13.0 g / 10 minutes MFI, thermally stable The agent-based composition is an additive; Example 7: Polypropylene with 13.0 g / 10 minutes of MFI, with the composition as an additive; Example 8: Polypropylene with 13.0 g / 10 minutes of MFI, stable against gas fading Example 9: Polyacrylamide with an MFI of 9.0 g / 10 minutes, with stability against gas fading. For a more detailed explanation, the results are shown in graphs and pictures. These display TF: • Figure 1 is a histogram showing the fracture energy, oven aging and abrasion according to the ratio of Example 2 with and without additives;-Figure 2 is the fracture energy, oven aging according to the ratio of Example 4 with and without additives And wear behavior; Figure 3a shows the wear behavior according to Example 1 (Comparative Example) without additives as a function of the number of manufactured codes; and-Figure 3b shows the wear behavior according to Example 8 (Specific examples) with additives Wear for the function. In Fig. 1, the left side of the pair represents the specific fracture energy, and the middle is the drying loss, according to Example 2 with and without additives. The left box is aging and the right is worn.
得結 磨損 潔。 200304510 ⑺ 麵_續買 對的右手方柱也顯示改良超過50%。比斷裂能，如左邊方 柱對的右手方柱所示，也較先前技藝改良。 圖2與圖1不同點在於其顯示根據實例4加及不加添加劑 之磨損。 . 圖3a顯示自純聚丙烯單纖維絲[對照試驗（實例製造· 米、200米及300米織品後，織機筘狀態之圖片。3〇〇米後聚 丙晞絨毛結垢得相當多，致織機必須停機。 圖3b顯示自根據本發明之單纖維絲[例證實例（實例8)]製 修 造100米、200米及300米織品後，織機筘狀態之圖片。甚至 在製造300米後所得絨毛量仍比對照實例ι〇〇米的為少。 測量方法： •溶體流動指數，根據ASTM D1238 ; •線密度，根據 SN 197 012及 SN 197 015 ，DIN 53830 補充； •自以下公式計算機械常數MC : MC。/D · F[cN/德士] _ 其中D代表伸長率，％及F代表長度，CN/德士。 磨損試驗之說明： 分段織軸（sectional beam)之製造。 刀&、我軸，各1〇〇〇米，係利用各種具體例之⑽個筒管之單 纖維絲製成。 編織試驗： 編織減驗係以織帶機進行。 最大可能生產：4〇〇〇 rpm ; -12- 200304510 (8) I發明說明續頁 梭口係由凸論形成； 工作模式：無緯線再進入； 經紗密度：22-80經紗/釐米； 筘： 開口，0.175毫米 筘齒厚度：0.264毫米 筘齒寬度：7.0毫米； 織機轉速：1000 rpm ;It has to be worn and clean. 200304510 面 __Continue to buy The right-handed square bar also shows an improvement of more than 50%. The specific fracture energy, as shown by the right-hand square column of the left square pair, is also improved over previous techniques. Figure 2 differs from Figure 1 in that it shows abrasion according to Example 4 with and without additives. Figure 3a shows a picture of the state of the loom after pure polypropylene monofilament filaments [control test (example manufacturing · meters, 200 meters, and 300 meters). Polypropylene yarn fluff after 300 meters is quite fouled, causing the loom The machine must be stopped. Figure 3b shows a picture of the loom state of the loom after fabricating 100 meters, 200 meters, and 300 meters of fabric from the single-fiber yarn [Illustrative Example (Example 8)] according to the present invention. It is still less than that of the comparative example. Measured method: • Melt flow index according to ASTM D1238; • Linear density according to SN 197 012 and SN 197 015, supplemented by DIN 53830; • Calculate the mechanical constant MC from the following formula : MC./D · F [cN / taxi] _ where D represents elongation,% and F represents length, CN / taxi. Description of abrasion test: Manufacturing of sectional beam. Knife & 1, our shafts, each 1000 meters, are made of single fiber filaments of various bobbins in various specific examples. Knitting test: The knitting reduction test is performed with a ribbon loom. The maximum possible production: 4,000 rpm; -12- 200304510 (8) I Description of the invention On the convex form; operating mode: no weft re-entry; warp density: 22-80 ends / cm; reed: opening, 0.175 mm dent thickness: 0.264 mm reed tooth width: 7.0 mm; loom speed: 1000 rpm;
編織速度：10米/時； 織紋：L 1/1薄布。 磨損行為評估： - 目視評估筘； - 重量測定所產生的絨毛。 為目視檢查，在100米、200米而較佳300米操作時間後將 筘拍照，並給予等級。Weaving speed: 10 meters / hour; Weaving pattern: L 1/1 thin cloth. Evaluation of abrasion behavior:-Visual evaluation of 筘;-Fluff produced by weight measurement. For visual inspection, the tadpoles will be photographed after 100m, 200m, and preferably 300m operation time, and graded.
利用重量法之磨損行為評估將說明於下。為進行評估， 收集300米操作時間後所形成的全部絨毛，予以秤重並利 以下公式使其與經紗重量發生關係： 沉積量％ =_絨毛沉積質量X 1 0 0 經紗數X經紗長度X線密度 10,000 根據本發明擁有直徑^ 0.050毫米之單纖維絲很適合製造 無磨損之過濾用織品。 藉由根據本發明之方法及根據本發明之單纖維絲，己可 首次編織實質上無任何磨損之聚丙晞單纖維絲及大幅提高 -13 - 200304510 (9) 發明說明續頁 織機之操作時間。此種單纖維絲係特別適合製造化學、製 藥及食品工業過濾用織品。 -14-The evaluation of the abrasion behavior using the gravimetric method will be described below. For evaluation, collect all the fluffs formed after 300 meters of operation time, weigh them and use the following formula to make them have a relationship with the weight of the warp yarns:% of deposition = _ pile fluff quality X 1 0 0 warp number X warp length X line Density 10,000 According to the present invention, a monofilament yarn having a diameter of ^ 0.050 mm is very suitable for the manufacture of non-abrasive filtering fabrics. By the method according to the present invention and the single fiber filament according to the present invention, it is possible for the first time to weave a polypropylene fiber monofilament yarn which is substantially free of any abrasion and greatly improve the operating time of the loom. This single-fiber yarn is particularly suitable for the manufacture of filter fabrics for the chemical, pharmaceutical and food industries. -14-