200909621 九、發明說明： 【發明所屬之技術領域】 本發明係關於具有優異強度·彈性率之高強度聚乙烯纖 維。進而詳言之，係關於即使不經多段拉伸步驟亦具有高 強度彈性率之高生產性的高強度聚乙烯纖維。 【先前技術】 習知對有機纖維之高強度化·高彈性率化有極多的硏 討，將由分子量高的彎曲性分子所成樹脂，以更高倍率進 行拉伸，以實現纖維之高強度化·高彈性率化之技術廣爲 周知。因此，關於此種技術之代表性紡紗方法方面，係以 超高分子量之聚乙烯爲原料，使用溶劑使超拉伸爲可行， 所謂"凝膠紡紗法（gel spinning)，1爲周知，已經廣泛用於產業 上（參照例如專利文獻1、專利文獻2)。由此種凝膠紡紗法 所得纖維，雖具有習知所無之優異強度·彈性率，因分子 量極高（因若不慢慢地拉伸則會裂斷），必須使拉伸速度降 低’成爲低速度且高倍率之拉伸，使得生產性極低，在工 業生產中多段拉伸爲必須，會有設備上需龐大費用之問題 產生。又’若非高倍率下之拉伸則無法實現高強度化，故 無法獲得單絲纖度大的高強度纖維，在以一定剛性爲必要 之用途中會有無法因應高單絲纖度化之要求之問題。 【專利文獻1】日本特公昭60-47922號公報 【專利文獻2】日本特公昭6 4 - 8 7 3 2號公報 【發明內容】 200909621 發明欲解決之課題 用來解決上述課題之有效手段係，不經多段拉伸步驟而 僅以一次之拉伸步驟來製造高強度聚乙烯纖維。本發明之 課題係提供一種，在如習知凝膠紡紗法之方法’可使達成 有困難之高生產性與高物性倂存之，高強度聚乙烯纖維及 其前驅物、以及前驅物之製造方法者。 解決課題之手段 本發明人等爲解決上述課題，經戮力硏究，結果終於完 成本發明。亦即本發明係，（1) 一種聚乙烯纖維，其特徵爲 由重覆單位實質上爲乙烯，極限黏度5dL/g以上之超高分 子聚乙烯所成，在束縛狀態中單絲之昇溫差式掃瞄熱量測 定（D S C曲線）之吸熱峰値全體面積與高溫側吸熱峰値之面 積比爲14.0=1.0〜1_5:1.0。（2)如（1)項之聚乙烯纖維，其 中使單絲在長度方向以每50cm分割，該被分割之每一單纖 維之束縛狀態中相對於昇溫DSC曲線之吸熱峰値全體面積 之，高溫側吸熱峰値面積之比率的變動係數（CV%)爲22% 以下。（3) —種聚乙烯複絲，其特徵爲由如（1)或（2)項之聚 乙烯纖維所成。（4)如（3 )項之聚乙烯複絲，其中該單絲 之D S C曲線之吸熱峰値全體面積與高溫側吸熱峰値面積之 比之單絲間變動係數（CV%)爲22%以下。（5)如（3 )或（4 ) 項之聚乙烯複絲，其中單絲之平均強度爲25cN/dtex以上。 (6)如（3 )至（5 )項中任一項之聚乙烯複絲，其中單絲 之平均纖度爲3.0dtex以上。（7) —種纖維前驅物，其特徵 200909621 爲具有實質上從中心至表層以羊肉串（shish kebab)構造作 爲基本單位之微細構造。（8) —種如（1)項之纖維之纖維前 驅物，其係以極限黏度[]爲5以上’重覆單位爲實質上 係由乙烯所成之高分子量聚乙烯爲主成分。（9) 一種纖維 前驅物之製造方法，其特徵爲將極限黏度[^]爲5以上’ 重覆單位爲由實質上乙烯所成之高分子量聚乙烯以5 wt% 以上未達50wt%之量溶解於揮發性有機溶劑’自噴嘴壓出 後，在高張力下一邊拉伸一邊通過揮發性之有機溶劑氣體 氛圍中，獲得具有實質上從中心至表層’以羊肉串構造作 爲基本單位之微細構造之纖維前驅物。 發明效果 因本發明可提供一種，生產性大幅提高之高強度聚乙烯 纖維。亦即，因可省略多段拉伸步驟，故在習知技術生產 性低的高強度聚乙烯纖維之生產性可予以提高，且可大幅 抑制設備投資，具有可提供廉價的高強度聚乙烯纖維之優 點。 又，在習知之凝膠紡紗技術，以多段拉伸步驟斷絲最多， 成爲生產性降低之原因。本發明之此種聚乙烯纖維，即使 未經過多段步驟因具有高彈性率、強度，故可使原單位飛 躍地提昇，而具有可提供生產性高的聚乙烯纖維之優點。 實施發明之最佳型態 以下，詳細說明本發明。 本發明之聚乙烯纖維，作爲其纖維前驅物（以下本發明之 200909621 纖維前驅物），實質上以使用具有使從中心至表層以羊肉串 (shish kebab)構造作爲基本單位之微細構造之物爲佳。在拉 伸前纖維前驅物之狀態下，藉由使羊肉串構造顯現，因而 可於低拉伸倍率·高拉伸速度獲得高強度·高彈性纖維。 由習知可知，爲提高拉伸性，適度調整纖維前驅物中分 子相互纏繞極爲重要，但本發明人等首先發現，在前驅物 之階段，藉由羊肉串構造之顯現，一方面可使纖維軸剖面 方向之分子相互纏繞大幅減低，一方面在纖維軸方向成爲 張緊的構造，藉此可獲得低拉伸倍率且高強度之纖維，且 可大幅提高拉伸速度。藉由成爲具有羊肉串構造之纖維前 驅物，而可得該等效果之理由並不明確，吾人推定在纖維 前驅物之階段，因爲羊肉串構造之串部分進行某一程度之 配向結晶化故可得低拉伸倍率且高強度化，另一方面因纖 維剖面方向之分子間接點少，故可提高拉伸速度。因此， 吾人認爲實質上具有從中心至表層全體羊肉串構造之情 形’易於拉伸，即使爲低拉伸倍率亦可使纖維內分子全體 充分拉伸，而有助於纖維之強度.彈性率。 在此’羊肉串構造係指近年來形成纖維微細構造之結晶 組織爲周知，係指例如如第1圖或第2圖所示在中心部分 貫通全體之如芯般之結晶部分，與將其以穿刺成串之方式 橫向切斷之折疊（folding )鏈所成薄層狀結晶所成形態之 意。 本發明之所謂羊肉串構造係指’可由纖維前驅物之6 0 0 200909621 倍以上TEM照片所確認之羊肉串構造，例如，如第 纖維表面所觀察到之，薄層與薄層互爲鍵結，形成 之構造’若改變一下看法，則羊肉串狀之構造互爲 並不含有可觀察到具網路構造般之構造。 又’本發明所謂之纖維前驅物，係指自紡紗嘴紡 取回輥取回，拉伸前之纖維狀樹脂或纖維狀溶劑與 合物之意。 本發明之具有實質上從中心至表層以羊肉串構造 本單位之微細構造的纖維前驅物，係在600倍ΤΕΜ 纖維軸垂直方向劃直線，在計數與此種直線交差之 構造時，含於從纖維軸中心至20%之範圍之支數（C) 層部20%之範圍所含支數（S)之比（C/S)，以0.8〜1.2 又，本發明之具有實質上從中心至表層以羊肉串 基本單位之微細構造之纖維前驅物，在400倍以上 片之纖維軸垂直方向劃直線’在計數與此種直線交 肉串構造時全體以存在50〜1〇0〇支爲佳。 本發明之纖維前驅物’係極限黏度[π ]5以上’其 位實質上由乙嫌所成高分子量聚乙嫌爲主成分者爲 種高分子量聚乙嫌，即使爲高分子量亦容易拉伸’ 可得高強度之潛力’因而爲適於達成本發明課題之 關於·本發明纖維前驅物之獲得方法，並無特別限 較佳的製造方法爲以極限黏度〔77〕5以上’其重 實質上由乙嫌所成尚分子量聚乙嫌以5wt%以上未達 3圖之 網眼狀 連接， 紗，以 樹脂混 作爲基 照片之 羊肉串 ，與表 爲佳。 構造爲 TEM照 差之羊 重覆單 佳。此 且具有 原料。 定，但 覆單位 [5 0 w t % 200909621 之量溶解於揮發性有機溶劑，自噴嘴壓出後， 力下拉伸，一邊通過揮發性之有機溶劑氣體氛 得具有實質上從中心至表層以羊肉串構造爲基 細構造之纖維前驅物。 本發明人等首先發現，爲獲得具有羊肉串構 驅物，在高張力取回，而顯現構造，且在緩和 化爲有效。但是，在用到溶劑之溶液紡紗之情 之顯現羊肉串構造之機制則極爲複雜，由於濃 使得顯現之做法並不相同。因此，在濃度不均 予高張力時，纖維前驅物內之構造成爲不均一 推薦在揮發性之有機溶劑氣體氛圍中藉由施予 可抑制表面溶劑蒸發，防止纖維（前驅物）內溶 生，可獲得具有實質上從中心至表層以羊肉串 單位之微細構造的纖維前驅物。 又，藉由在高張力取回所形成之羊肉串構造 緩和等所致消失，故在急遽且均一地冷卻時以 1000°C /S以上爲佳。更佳爲300(TC /S以上。若 速度，因而可在纖維前驅物內部形成均一且有 構造。 又，如此一來爲使冷卻速度提高，吾人推薦 使用導熱係數（heat conductivity)大的液體。其 溶劑爲非相溶之液體爲佳。若與溶劑非相溶時 層溶劑之萃取，因而可使纖維前驅物內溶劑 一邊在高張 圍中，以獲 本單位之微 造之纖維前 之前迅速固 形，本發明 度之狀態， 一之狀態施 。因此吾人 高張力，而 劑濃度斑發 構造爲基本 ，因可防止 冷卻速度爲 爲此種冷卻 效地羊肉串 冷卻介質可 中以使用之 ，可抑制表 度於均一狀 -10- 200909621 態下固化。例如，就簡便性而言可推薦水。 本發明之纖維前驅物之製造方法以其原料之高分子量聚 乙嫌之極限黏度[7?]爲5dl/g以上爲佳，更佳爲gdl/g以上， 還要更佳爲10dl/g以上。極限黏度[77]未達5時，會無法 獲得所望強度，例如無法獲得超過強度25cN/dtex之高強度 纖維之情形。一方面，就上限而言，若可得所望之強度的 範圍則並無特別問題，但聚乙烯之極限黏度[77 ]以35以下 爲佳，更佳爲30以下，還要更佳爲25以下。極限黏度過 高時，加工性降低造成纖維化之困難。 本發明中超高分子量聚乙烯，其特徵爲重覆單位實質上 係乙烯，少量之其他單體，例如α-烯烴、丙烯酸及其衍生 物、甲基丙烯酸及其衍生物、乙烯矽烷及其衍生物等共聚 物亦可，該等共聚合物彼此之間，或與乙烯單獨聚合物之 共聚物，進而可與其他α-烯烴等同元聚合物之掺合體。尤 其是使用丙烯、丁烯-1等α烯烴與共聚物而使短鏈或長鏈 之分支鏈含有某一程度，在製造本纖維上，尤其是在紡紗/ 拉伸中可賦予製絲上之穩定爲更佳。但是若乙烯以外之含 量增加過多時反而成爲拉伸之阻礙要因，故就可得高強度/ 高彈性率纖維之觀點而言，α -烯烴等其他單體，單體單位 以0.2莫耳％以下爲佳，更佳爲〇. 1莫耳％以下。當然亦可 爲乙烯單獨之同元聚合物。 本發明之纖維前驅物之可推薦之製造方法中，此種高分 子量之聚乙烯係使用十氫萘/四氫化萘等之揮發性有機溶 -11 - 200909621 劑進行溶解爲佳。在常溫固體或非揮發性之溶劑，要提高 拉伸速度則有困難，或因溶劑萃取步驟爲必要，故與使用 有機溶劑之情形比較生產性變低。溶解之際之濃度以 30wt%以下爲佳，更佳爲20wt%以下，最佳爲I5wt%以下。 所使用之該混合摻雜’可以各種方法，例如將固體聚乙 烯懸浮於溶劑中，同時在高溫進行攪拌，或將該懸濁液藉 由使用具備混合及搬運部之2軸螺旋壓出機來製造。 本發明之纖維前驅物之製造方法中使該混合摻雜通過排 列有複數噴絲孔（orifice)所成噴嘴成爲摻雜絲爲佳。對摻雜 絲變換之際之溫度，應在溶解點以上設定。此溶解點當然 仰賴於選擇的溶劑、濃度及聚乙烯之wt%，以至少140°C以 上爲佳，更佳爲150°C以上。此溫度以在該聚乙烯之分解溫 度以下設定爲佳。 接著，就用以獲得本發明之高強度聚乙烯纖維而爲適當 的纖維前驅物之製造方法中重要的因素加以說明。 將自噴嘴排出之排出凝膠絲狀，一邊在高張力下拉伸一 邊通過揮發性之有機溶劑氣體氛圍中爲緊要。此時有機溶 劑氣體濃度爲5g/m3以上，較佳爲10g/.m3以上’特佳爲 20g/m3以上。在未達5g/m3之情形，如第3圖在纖維表層部 難以顯現羊肉串構造，而在快速變形速度之拉伸，斷絲頻 頻發生使生產性降低，或表層部造成缺陷而降低強度。 又，高張力下係指，將外加於排出凝膠絲狀之張力値除 以聚合物換算之纖度之値，其爲0.28cN/dtex以上、未達 -12- 200909621 0.50cN/dtex，較佳爲 0.30cN/dtex 以上、未達 〇.48cN/dtex， 特佳爲 0.32cN/dtex以上、未達0.45cN/dtex。張力未達 0.28cN/dtex時，從中心部至表層部無法形成均一的羊肉串 構造，在低拉伸倍率無法獲得高強度。反之在〇.5〇cN/dtex 以上拉伸時產生該凝膠絲狀之裂斷使生產性變差。 吾人考慮要使張力提高，就得使取回速度提高，使紡紗 噴嘴孔徑變大，紡紗後使表示黏性之區間縮短等之方法。 又，在熔融紡紗中，可藉由使紡紗後之氛圍溫度變低來使 張力一般地變高，而在使用溶劑之情形，若使氛圍溫度降 低時可抑制溶劑之蒸發，相反地亦有使張力變高之情形， 而爲複雜。 本發明之聚乙烯纖維，係在束縛狀態中單絲之昇溫差式 掃瞄熱量測定（D S C曲線）之吸熱峰値全體面積與高溫側之 吸熱峰値之面積之比，以14.0:1.0〜1.5:1.0爲佳。本發明 之高強度聚乙烯纖維，其昇溫DSC曲線在140。(：〜150。(：（低 溫側）之溫度區域顯示至少1條吸熱峰値，又在1 5 0 t〜1 6 0 °C (高溫側）之溫度區域顯示至少1條吸熱峰値。 該等峰値，係低溫側之峰値表示高強度聚乙烯纖維之斜 方晶的熔融峰値，及表示自斜方晶至六方晶之轉移峰値， 高溫側之峰値係表示高強度聚乙烯纖維之六方晶之熔融峰 値（參照例如「Tashiroet等人；巨分子，29,7460(1996)」文獻。 經本發明人戮力硏討結果首先發現六方晶之熔融峰値之面 積’與纖維中串構造數目之相關性強，六方晶之熔融峰値 -13- 200909621 之面積越大，則纖維中串構造之數變多。亦即此表示，相 對於吸熱峰値全體面積’高溫側之吸熱峰値之面積比率越 大，則在纖維內串構造有越多數形成。 本發明人等，係使羊肉串構造以纖維前驅物之狀態顯 現，使其以拉伸步驟使大部分成爲串構造（使羊肉部分消 失），藉此可得具有高強度·彈性率之聚乙烯纖維。吾人推 測此係，串構造可有效地有助於強度·彈性率，而提高串 構造之密度的效果。一方面，超過上述範圍之串構造多的 ' 聚乙烯纖維對強度.彈性率助力變小，而另一方面，單絲 切斷，或後步驟中斷絲易於發生。更佳爲’吸熱峰値全體 面積與高溫側之吸熱峰値之面積之比爲 1 2.0 : 1.0〜 3.0:1.0，進而較佳爲 11.0=1.0 〜5.0:1.0。 在此，昇溫DSC曲線係在單絲50cm於施加纖度（dtex)x 1/1 0(g)之負荷之狀態，成爲在鋁板無鬆弛部分之束縛狀 態，在惰性氣體下，於1 0 °C /分之升溫速度使溫度自室溫上 ( 升至200乞而得。此外，吸熱峰値係僅採用峰値溫度可正確 讀取者，在修正所得昇溫DSC曲線之基線後’讀取峰値溫 度。又，使用GALACTIC工業公司製軟體GRAMS/32第四 版，進行波形分離處理，計算吸熱峰値全體之面積’及高 溫側之吸熱峰値之面積，求得吸熱峰値全體面積與高溫側 之吸熱峰値之面積比。在此，基線係指，如塑膠之轉移溫 度測定方法（〗ISK7 1 2 1)所揭示，對試驗試料於不產生轉移及 反應之區域的D S C曲線。 -14- 200909621200909621 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a high-strength polyethylene fiber having excellent strength and modulus of elasticity. Further, in detail, it is a high-strength polyethylene fiber having high productivity and high modulus of elasticity even without a multi-stage stretching step. [Prior Art] It is known that the high strength and high elastic modulus of organic fibers are extremely high, and the resin is formed from a bendable molecule having a high molecular weight, and is stretched at a higher magnification to achieve high strength of the fiber. The technology of high-elasticity is well known. Therefore, regarding the representative spinning method of this technology, it is possible to use ultra-high molecular weight polyethylene as a raw material and use a solvent to make super-stretching possible. The so-called "gel spinning method, 1 is well known. It has been widely used in industry (see, for example, Patent Document 1 and Patent Document 2). The fiber obtained by such a gel spinning method has an excellent strength and elastic modulus which are not known at all, and the molecular weight is extremely high (it is broken if it is not stretched slowly), and the stretching speed must be lowered' It becomes a low-speed and high-magnification stretch, which makes the productivity extremely low. In the industrial production, multi-stage stretching is necessary, and there is a problem that a large cost is required on the equipment. In addition, if it is not stretched at a high magnification, high strength cannot be achieved, so that high-strength fibers having a large single-filament fineness cannot be obtained, and there is a problem that it is impossible to cope with the requirement of high monofilament fineness in applications requiring a certain rigidity. . [Patent Document 1] Japanese Patent Publication No. Sho 60-47922 [Patent Document 2] Japanese Patent Publication No. Sho 6 4 - 8 7 3 2 [Invention Summary] 200909621 The object to be solved by the invention is an effective means for solving the above problems. High strength polyethylene fibers are produced in only one stretching step without a multi-stage stretching step. SUMMARY OF THE INVENTION An object of the present invention is to provide a high-strength polyethylene fiber, a precursor thereof, and a precursor in a method such as a conventional gel spinning method, which can achieve high productivity and high physical properties which are difficult to achieve. Manufacturing method. MEANS TO SOLVE THE PROBLEM In order to solve the above problems, the inventors of the present invention have finally found out the cost of the invention. That is, the present invention is a (1) polyethylene fiber characterized by a super-high molecular polyethylene having a repeating unit of substantially ethylene and an ultimate viscosity of 5 dL/g or more, and a difference in temperature rise of the monofilament in a restrained state. The area ratio of the endothermic peak of the scanning heat measurement (DSC curve) to the endothermic peak of the high temperature side was 14.0 = 1.0 to 1_5: 1.0. (2) The polyethylene fiber according to (1), wherein the monofilament is divided every 50 cm in the longitudinal direction, and the total area of the endothermic peak of the temperature-increasing DSC curve in the bound state of the divided single fiber is The coefficient of variation (CV%) of the ratio of the endothermic peak area on the high temperature side is 22% or less. (3) A polyethylene multifilament characterized by being formed of a polyethylene fiber as in (1) or (2). (4) The polyethylene multifilament according to item (3), wherein a ratio of the coefficient of variation (CV%) between the entire area of the endothermic peak of the DSC curve of the monofilament and the area of the endothermic peak of the high temperature side is 22% or less. . (5) The polyethylene multifilament of (3) or (4), wherein the average strength of the monofilament is 25 cN/dtex or more. (6) The polyethylene multifilament according to any one of (3) to (5), wherein the monofilament has an average fineness of 3.0 dtex or more. (7) - Fiber precursor, which is characterized by a fine structure having a structure of a shish kebab substantially as a basic unit from the center to the surface layer. (8) A fiber precursor of the fiber of the item (1), which has an ultimate viscosity [] of 5 or more. The repeating unit is substantially composed of a high molecular weight polyethylene composed of ethylene. (9) A method for producing a fiber precursor, characterized in that the ultimate viscosity [^] is 5 or more. 'The repeating unit is a high molecular weight polyethylene composed of substantially ethylene, and the amount is 5 wt% or more and less than 50 wt%. After being dissolved in a volatile organic solvent, after being extruded from a nozzle, it is stretched under high tension and passed through a volatile organic solvent gas atmosphere to obtain a fine structure having a mutton string structure substantially as a basic unit from the center to the surface layer. Fiber precursor. EFFECT OF THE INVENTION According to the present invention, it is possible to provide a high-strength polyethylene fiber which is greatly improved in productivity. That is, since the multi-stage stretching step can be omitted, the productivity of the high-strength polyethylene fiber which is low in productivity in the prior art can be improved, and the investment in equipment can be greatly suppressed, and the high-strength polyethylene fiber which can provide inexpensive can be provided. advantage. Further, in the conventional gel spinning technique, the yarn breakage is the largest in the multi-stage drawing step, which causes a decrease in productivity. The polyethylene fiber of the present invention can greatly improve the original unit even if it has a high modulus of elasticity and strength without excessive steps, and has the advantage of providing a highly productive polyethylene fiber. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyethylene fiber of the present invention, as a fiber precursor (hereinafter, the 200909621 fiber precursor of the present invention), is substantially a material having a fine structure having a shish kebab structure as a basic unit from the center to the surface layer. good. In the state in which the fiber precursor is stretched, the kebab structure is visualized, so that high-strength and high-elastic fibers can be obtained at a low draw ratio and a high draw speed. It is known from the prior art that in order to improve the stretchability, it is extremely important to appropriately adjust the intertwining of molecules in the fiber precursor, but the inventors first found that at the stage of the precursor, by the appearance of the mutton string structure, the fiber can be made on the one hand. The entanglement of the molecules in the axial direction of the shaft is greatly reduced, and on the other hand, the structure is tensioned in the fiber axis direction, whereby fibers having low draw ratio and high strength can be obtained, and the stretching speed can be greatly increased. The reason why these effects can be obtained by becoming a fiber precursor having a mutton string structure is not clear, and it is presumed that at the stage of the fiber precursor, since the string portion of the mutton string structure is subjected to a certain degree of alignment crystallization, The tensile strength is low and the strength is increased. On the other hand, since the molecular indirect points in the fiber cross-sectional direction are small, the stretching speed can be increased. Therefore, we believe that it is easy to stretch from the center to the entire kebab structure of the surface layer. Even the low stretching ratio can fully stretch the fibers in the fiber, which contributes to the strength of the fiber. . Here, the 'mutton string structure' refers to a crystal structure in which a fine fiber structure is formed in recent years, and is a core-like crystal portion that penetrates the entire portion in the center portion as shown in FIG. 1 or FIG. 2, for example, and The shape of the thin layered crystal formed by the folding of the folded chain in the manner of puncturing into a string. The so-called mutton string structure of the present invention refers to a mutton string structure which can be confirmed by a TEM photograph of a fiber precursor of 60 0 200909621 times, for example, as observed on the surface of the first fiber, the thin layer and the thin layer are bonded to each other. , the formation of the structure 'If you change the view, the mutton-like structures do not contain a structure that can be observed with a network structure. Further, the term "fiber precursor" as used in the present invention means a fiber-like resin or a fibrous solvent compound which is taken back from the spinning nozzle and taken back by the spinning nozzle. The fiber precursor of the present invention having a fine structure in which the unit is substantially constructed from the center to the surface layer of the mutton string is drawn in a straight line in the vertical direction of the fiber axis of 600 times, and is included in the structure in which the line intersects with such a line. The number of the fiber axis center to the range of 20% (C) The ratio of the number of branches (S) in the range of 20% of the layer portion (C/S) is 0.8 to 1.2, and the present invention has substantially from the center to The fiber precursor of the fine structure of the basic unit of mutton string is drawn in a straight line in the vertical direction of the fiber axis of 400 times or more. In the counting and the straight line of the meat skewer structure, it is better to have 50~1〇0〇. . The fiber precursor of the present invention has an ultimate viscosity [π ] 5 or more. The position is substantially suspected of being a high molecular weight polyethylene, and is considered to be a high molecular weight polyethylene. Even if it is a high molecular weight, it is easy to stretch. 'The potential for obtaining high strength' is thus a method for obtaining the fiber precursor of the present invention which is suitable for achieving the subject of the present invention, and there is no particular limitation that the preferred method of manufacture is to have an ultimate viscosity of [77] 5 or more. It is better to use a mesh-like connection of 5 wt% or more and less than 3 graphs, and a kebab with a resin mixture as a base photograph. Constructed as a TEM illuminating sheep, repeating the single. This has raw materials. Set, but the cover unit [5 0 wt % 200909621 is dissolved in a volatile organic solvent, after being pressed out of the nozzle, the force is stretched, and the volatile organic solvent gas has a substantially mutton from the center to the surface layer. The string is constructed as a fibrous precursor of a fine structure. The inventors of the present invention first found that in order to obtain a mutton string structure, it is retrieved at a high tension, and the structure is revealed, and the mitigation is effective. However, the mechanism of kebab formation in the case of spinning with a solvent solution is extremely complicated, and the practice of appearance is not the same due to the concentration. Therefore, when the concentration is uneven and the tension is high, the structure in the fiber precursor becomes uneven. It is recommended to inhibit the evaporation of the surface solvent by the application in the volatile organic solvent gas atmosphere to prevent the fiber (precursor) from being dissolved. A fiber precursor having a fine structure of mutton units substantially from the center to the surface layer can be obtained. Further, since the structure of the mutton string formed by the high tension retrieval disappears, it is preferably 1000 ° C / S or more in the case of rapid cooling and uniform cooling. More preferably, it is 300 (TC / S or more. If the speed is high, it can be formed uniformly inside the fiber precursor and has a structure. Further, in order to improve the cooling rate, it is recommended to use a liquid having a large heat conductivity. The solvent is preferably a non-compatible liquid. If the solvent is not miscible with the solvent, the solvent in the fiber precursor can be rapidly solidified before the fiber is obtained in the high-tension zone. The state of the invention is in the state of one. Therefore, the high tension of the person, and the concentration of the agent concentration is basic, because the cooling rate can be prevented from being used for the cooling effect of the mutton string cooling medium, which can be suppressed. The degree of solidification is in the form of uniformity-10-200909621. For example, water can be recommended for simplicity. The method for producing the fiber precursor of the present invention is based on the high viscosity of the raw material, and the ultimate viscosity [7?] 5 dl / g or more is preferred, more preferably gdl / g or more, and even more preferably 10 dl / g or more. When the ultimate viscosity [77] is less than 5, the desired strength cannot be obtained, for example, the excess strength is not obtained at 25 cN/ In the case of high-strength fibers of dtex, on the one hand, there is no particular problem with respect to the upper limit, but the ultimate viscosity of polyethylene [77] is preferably 35 or less, more preferably 30 or less. More preferably, it is 25 or less. When the ultimate viscosity is too high, the workability is lowered to cause difficulty in fiberization. In the present invention, the ultrahigh molecular weight polyethylene is characterized in that the repeat unit is substantially ethylene, and a small amount of other monomers, for example Copolymers of α-olefins, acrylic acid and derivatives thereof, methacrylic acid and derivatives thereof, vinyl decane and derivatives thereof, copolymers of these copolymers with each other, or with ethylene alone polymers, a blend of other α-olefin equivalent polymers. In particular, an alpha olefin such as propylene or butene-1 is used to copolymerize a short chain or a long chain branch to a certain extent, in the production of the fiber. In particular, it is preferable to impart stability to the spinning in the spinning/stretching. However, if the content other than ethylene is excessively increased, it becomes a hindrance to stretching, so that a high strength/high modulus fiber can be obtained. In other words, the monomer unit such as α-olefin is preferably 0.2 mol% or less, more preferably 0.1 mol% or less. It may of course be a homopolymer of ethylene alone. The fiber precursor of the present invention. In the recommended manufacturing method, the high molecular weight polyethylene is preferably dissolved using a volatile organic solvent -11 - 200909621 agent such as decalin/tetrahydronaphthalene. It is a solid or nonvolatile solvent at normal temperature. It is difficult to increase the stretching speed, or the solvent extraction step is necessary, so that the productivity is lower than in the case of using an organic solvent. The concentration at the time of dissolution is preferably 30% by weight or less, more preferably 20% by weight or less. It is preferably I5 wt% or less. The mixed doping used may be carried out by various methods, for example, suspending solid polyethylene in a solvent while stirring at a high temperature, or using the mixing and carrying portion by using the suspension. It is manufactured by a 2-axis screw extruder. In the method for producing a fiber precursor of the present invention, it is preferred that the mixed doping is made into a doped wire by a nozzle in which a plurality of orifices are arranged. The temperature at which the doped filament is converted should be set above the dissolution point. This dissolution point of course depends on the solvent, concentration and wt% of the polyethylene, preferably at least 140 ° C, more preferably 150 ° C or higher. This temperature is preferably set below the decomposition temperature of the polyethylene. Next, an important factor in the production method of a suitable fiber precursor will be described in order to obtain the high-strength polyethylene fiber of the present invention. It is important that the discharged gel discharged from the nozzle is filament-shaped and stretched under a high tension while passing through a volatile organic solvent gas atmosphere. The concentration of the organic solvent gas at this time is 5 g/m3 or more, preferably 10 g/m3 or more, and particularly preferably 20 g/m3 or more. In the case of less than 5 g/m3, as shown in Fig. 3, it is difficult to visualize the kebab structure at the surface layer of the fiber, and at the speed of rapid deformation, the frequency of the broken wire frequently occurs to lower the productivity, or the surface portion causes defects and reduces the strength. Further, the high tension means that the tension applied to the filaments of the discharged gel is divided by the denier of the polymer conversion, which is 0.28 cN/dtex or more and less than -12 to 200909621 0.50 cN/dtex, preferably. It is 0.30 cN/dtex or more, less than .48 cN/dtex, particularly preferably 0.32 cN/dtex or more, and less than 0.45 cN/dtex. When the tension is less than 0.28 cN/dtex, a uniform kebab string structure cannot be formed from the center portion to the surface layer portion, and high strength cannot be obtained at a low draw ratio. On the other hand, when the 〇.5〇cN/dtex is stretched or more, the gel-like cleavage is generated to deteriorate the productivity. When we consider the tension to be increased, the retracting speed is increased, the diameter of the spinning nozzle is increased, and the interval indicating the viscosity is shortened after spinning. Further, in the melt spinning, the tension can be generally increased by lowering the temperature of the atmosphere after spinning, and in the case of using a solvent, evaporation of the solvent can be suppressed when the temperature of the atmosphere is lowered, and conversely There are situations in which the tension is raised, and it is complicated. The polyethylene fiber of the present invention is a ratio of the endothermic peak of the temperature rise differential scanning calorimetry (DSC curve) of the monofilament in the bound state to the area of the endothermic peak of the high temperature side, in the range of 14.0: 1.0 to 1.5. : 1.0 is better. The high strength polyethylene fiber of the present invention has a DSC curve at 140. (: ~150. (: (low temperature side) The temperature area shows at least one endothermic peak, and at least one endothermic peak is displayed in the temperature range of 150 to 1600 °C (high temperature side). The peak of the isothermal peak, the peak of the low temperature side, indicates the melting peak of the orthorhombic crystal of the high-strength polyethylene fiber, and the peak of the transition from the orthorhombic to the hexagonal crystal, and the peak of the high temperature side indicates the high-strength polyethylene. The melting peak of the hexagonal crystal of the fiber (refer to, for example, "Tashiroet et al.; Giant Molecules, 29, 7460 (1996)". The inventors of the present invention first discovered the area of the melting peak of the hexagonal crystal and the fiber. The correlation between the number of string structures is strong, and the larger the area of the melting peak of hexagonal crystal 値-13-200909621, the greater the number of string structures in the fiber. That is to say, the heat absorption peak of the entire area relative to the endothermic peak ' The larger the area ratio of the peaks, the more the string structure is formed in the fiber. The inventors of the present invention have made the mutton string structure appear in the state of the fiber precursor, so that most of the string structure is formed by the stretching step ( Make the mutton partially disappear) A polyethylene fiber having a high strength and an elastic modulus is obtained. It is assumed that the string structure can effectively contribute to the strength and the modulus of elasticity, and the effect of increasing the density of the string structure. On the other hand, the string structure exceeding the above range is large. 'Polyethylene fiber contributes less strength to the elastic modulus. On the other hand, the monofilament is cut, or the subsequent step interrupts the filament easily. It is more preferably the area of the endothermic peak and the endothermic peak of the high temperature side. The ratio is 1 2.0: 1.0 to 3.0: 1.0, and more preferably 11.0 = 1.0 to 5.0: 1.0. Here, the temperature rising DSC curve is at a load of 50 cm of the monofilament at a applied denier (dtex) x 1/1 0 (g). The state is in a state in which the aluminum plate has no slack portion, and the temperature is raised from room temperature (up to 200 在 at a temperature increase rate of 10 ° C /min under an inert gas. In addition, the endothermic peak system only uses a peak.値The temperature can be read correctly. After correcting the baseline of the obtained heating DSC curve, the peak temperature is read. In addition, the software GRAMS/32 fourth edition of GALACTIC Industrial Co., Ltd. is used to perform waveform separation processing to calculate the endothermic peak. Area 'and high temperature side suction The area of the peak, the ratio of the area of the endothermic peak to the endothermic peak of the high temperature side. Here, the baseline refers to the test sample, as disclosed in the method for measuring the transfer temperature of plastics (ISK7 1 2 1). DSC curve in the area where no transfer and reaction occurs. -14- 200909621
又，吸熱峰値全體面積，係表示DSC曲線與圍繞於所內 插（Interpolation )之基線部分的面積，高溫側之吸熱峰 値之面積係表示150度〜160°C之溫度區域（高溫側）之DSC 曲線之峰値與圍繞於所內插之基線之部分的面積。在此塑 膠轉移溫度測定方法UIS K7121)，峰値之定義係指在DSC t 曲線中，曲線自基線脫離再次回到基線之部分，但在本發 明係將所得昇溫D S C曲線予以微分僅使微分値自正變至負 之情形作爲峰値。 本發明之聚乙烯纖維之製造方法並無特別限定，但對具 有前述均一羊肉串構造之纖維前驅物而言，期望在降低溶 劑濃度之狀態中使拉伸倍率提高。在溶劑濃度低的狀態以 高倍率拉伸時可有效地顯現串構造（羊肉部分消失）者係由 本發明人等首先發現。具體言之，可例舉在纖維前驅物取 回輥與（一段）拉伸絲取回輥之間設置驅動輥，藉由調節相 關驅動輥之速度，在纖維前驅物取回輥與驅動輥間可使溶 劑濃度降低，同時可使驅動輥與拉伸絲纏繞輥間之拉伸倍 率提高之方法。吾人推測在不設置驅動輥下進行拉伸時， 黏度低的部分，亦即在溶劑濃度高的部分因會變形而難以 形成串構造。 又，因此種拉伸手段亦可達成單絲間拉伸誤差變小之效 果。亦即，在（第一段）拉伸步驟，溶劑一邊蒸發一邊拉伸， 但在複絲之情形，於拉伸區域自位於捆（bundle)表層之單絲 進行溶劑之蒸發，在單絲間溶劑濃度之測定偏差爲大的狀 -15- 200909621 態下進行拉伸時，根據上述方法，在單絲間之溶劑濃度差 變小的狀態因而成爲以高拉伸倍率拉伸。 本發明之聚乙烯纖維，係使單絲在長度方向以每5 0 c m分 割，在該經分割之每一單纖維之束縛狀態中相對於昇溫 D S C曲線之吸熱峰値全體面積，高溫側之吸熱峰値面積之 比率變動係數（CV%)以22%以下爲佳。若爲此種聚乙烯纖 維’在作爲實用之複絲的情形，取決於面積比率最小的部 位而決定複絲全體強度，結果一方面複絲之強度變高，一 方面可得到單絲斷絲或在後步驟之斷絲少的複絲。更佳之 CV%爲17%，特佳爲12%以下。 CV%之下限並無特別限定，即使低於1 %亦可，對強度等 之影響則幾乎觀測不到。另外，CV%係以下式定義。 CV% = l〇〇x標準偏差/平均値（％) 獲得此種聚乙烯纖維之手段並無特別限定，在作爲冷卻 介質使用液體之情形，以使液面變動儘可能變小爲佳。經 本發明人等戮力硏討，結果爲了獲得本發明生產性高的高 強度聚乙烯纖維，以使液面變動成爲1.0mm以下爲佳。液 面變動超過1.0mm時’在單絲之長度方向及單絲間中該氣 體介質空間之通過時間的變動變的顯著，單絲之構造在長 度方向及後述單絲間顯著變的不均一。尤其是在液面變動 劇烈之情形，在該氣體介質空間中單絲裂斷。 本發明之聚乙烯纖維可爲複絲，該單絲之D S C曲線之吸 熱峰値全體面積與高溫側之吸熱峰値之面積之比之單絲間 -16- 200909621 變動係數（C V % )以2 2 %以下爲佳。更佳爲丨7 %以下，特佳爲 1 2 %以下。高溫側吸熱峰値面積比率之比率，即使較複絲全 體之平均爲咼’在單絲間之均一性變差的話，由於紗線全 體的強度取決在面積比率最小的單絲，而難以得到高強度 纖維。另一方面，在後步驟中就斷絲而言，亦大爲取決在 面積比率最大的單絲。因此，藉由使複絲之單絲間之c V % 在上述範圍內，可獲得強度高，且後加工通過性優異之複 絲。單絲間CV%之下限並無特別限定，即使比1%爲低，效 果亦幾乎不變。 此種獲得單絲間之C V %低的複絲之製造方法並無特別限 定，但在製造該纖維前驅物之際，較佳使紡紗嘴正下方之 氛圍溫度呈均一。經本發明人等戮力硏討結果，在紡紗嘴 正下方使單絲間氛圍溫度差爲±3.0°c以下，較佳爲±2.0°C以 下，更佳爲± 1 · 〇 °C以下，可使單絲間構造差成爲極小，可 知製造本發明之生產性高的高強度聚乙烯爲可行的。再者 在同一場所藉由使經過時間之氛圍溫度差爲± 3.0 °C以下， 較佳爲±2.0°C以下’更佳爲±1.0°C以下，可使單絲長度方向 之構造差成爲極小，可製成本發明之生產性高的高強度聚 乙烯爲自明。 又，如前述’在拉伸步驟中，在纖維前驅物收回輥與拉 伸絲收回輥之間設置驅動輥，藉由該驅動輥速度之調節’ 在溶劑濃度低的狀態中可提高拉伸倍率使單絲間拉伸呈均 一爲佳。 -17- 200909621 在本發明人等所硏討之範圍，該驅動輥通過時纖維前驅 物之溶劑濃度以3 0 %以下爲佳。更佳爲2 5 %以下，特佳爲 2 0 %以下。 本發明之聚乙烯複絲，用來與習知物比較生產性可飛躍 地提高，進而若爲纖度50.0dtex〜lOOOdtex，單絲纖度 l_6dtex〜250dtex之情形，尤其可發揮顯著的效果。 亦即，在低拉伸倍率因具有高強度.高彈性率，可提高 單絲纖度’又因單絲間測定偏差爲小故即使在高複絲之纖 度中亦爲高性能。若爲此種範圍之纖度、單絲纖度，例如 在要求剛性或耐磨耗性之釣魚線或手套等多數之用途而可 提高其性能。更佳爲，纖度130dtex〜5 00dtex，單絲纖度 2.0dtex〜180dtex，特佳爲纖度I50dtex〜460dtex，單絲纖 度 5.0dtex〜130dtex 。 本發明中聚乙烯複絲之平均強度以25cN/dtex以上爲 佳，更佳爲27cN/dtex以上。平均強度未達25cN/dtex之情 形，在製成應用製品時，會有作爲製品之強度不足之可能 性。 【實施方式】 以下就關於本發明中特性値之測定法及測定條件加以說 明。 (極限黏度） 在135Ό之十氫萘藉由烏別洛德（Ubbelohde)型毛細黏度 管來測定各種稀溶液之比黏度，以相對於其黏度之濃度而 -18- 200909621 描繪之最小平方近似（least square approximation)所得直 線之對原點的外插點來決定極限黏度。在測定之際，分割 或切斷樣本使樣本成爲約5mm之長度，對聚合物添加lwt %抗氧化劑（商標名「Yoshinox BHT」，吉富製藥製），在 1 3 5 °C經4小時攪拌溶解來調整測定溶液。 (複絲之強度/伸度/彈性率） 本發明中強度、彈性率係使用東方科技公司製 「TENSILON」，在試料長200mm(夾盤間長度）、伸長速度 100%/分之條件下使應力-應變曲線（stress-strain curve)在 氛圍溫度20°C、相對濕度65 %之條件下測定，自於裂斷點 之應力與延伸來計算強度（cN/dtex)，自賦予伸度（％)、曲線 之原點附近最大傾斜度的接線來計算彈性率（cN/dtex)而求 得。此外，各値係使用1 0次測定値之平均値。 (差式掃瞄熱量計測定） 差式掃瞄熱量計測定係使用Perkin Elmer公司製「DSC7 型」。以施加纖度（dtex) X 1/1 0(g)之負荷於單絲50cm之狀 態下，成爲在鋁板無鬆弛部分之束縛狀態，惰性氣體下’ 以1(TC /分之昇溫速度自室溫升溫至200°C，求得昇溫DSC 曲線。修正所得昇溫D S C曲線之基線後，讀取峰値溫度。 又進行波形分離處理，計算吸熱峰値全體之面積’及高溫 側吸熱峰値之面積，求得吸熱峰値全體面積’與咼溫側吸 熱峰値面積之比。在波形分離係使用galactic工業公司 製軟體GRAMS/32第4版。又，在求得單絲間及單絲長度 -19- 200909621 方向之該面積比率之情形，係使測定單絲數爲n = 20 ’於施 加纖度（dtex) X l/10(g)之負荷於單絲50cm之狀態’成爲 在鋁板無鬆弛部分之束縛狀態，在惰性氣體下’以1 0 °C / 分之昇溫速度自室溫升溫至200°C ’求得昇溫DSC曲線。 在修正所得昇溫D S C曲線之基線後，讀取峰値溫度。又， 進行波形分離處理，計算吸熱峰値全體面積’及高溫側之 吸熱峰値面積，在求得每一單絲之吸熱峰値全體面積與高 溫側吸熱峰値面積之比後依照下述之式求得CV %。 f % CV% = 100X標準偏差/平均値（％) (實施例1) 將極限黏度20.OdL/g之超高分子量聚乙烯與十氫萘以重 量比8 : 9 2混合來形成漿液狀液體。將該物質以具備混合及 運送部之2軸螺旋壓出機溶解，自所得透明的均一物質排 列成圓形之孔數48個、直徑〇· 8mm之噴絲孔以2· 5 g/分壓 出。將該壓出溶解物質’透過以構件被覆之長度8.〇mm之 , 氣體介質空間，藉由通過以恆定流之水所充滿之圓筒狀流 管（以厚度5mm之耐熱玻璃被覆之外部空間所遮蔽）’使液 面變動抑制於〇.5mm以下，且由該壓出溶解物質突入水面 之部位將累積於液面之十氫萘予以連續除去同時均一地冷 卻，使該壓出溶解物質中之溶劑並不自該壓出溶解物質除 去，而以紡紗速度30m/min取回凝膠絲狀。接著’並不將 該凝膠纖維纏繞而在氮加熱烤爐中’使用驅動輥乾燥該凝 膠纖維中殘留溶劑濃度至1 〇 %爲止後以11倍之拉伸比進行 -20- 200909621 拉伸。所得聚乙烯纖維之諸物性如表1所示。 (實施例2) 將極限黏度20.OdL/g之超高分子量聚乙烯與 量比1 0 : 90混合而形成漿液狀液體。以具備混 之2軸螺旋壓出機使該物質溶解，自所得透明 排列成圓形之孔數 30個，直徑 0.8mm之【 2.5g/min壓出。將該壓出溶解物質，透過以構 度1 0mm之氣體介質空間，藉由通過以恆定流 k 之圓筒狀流管（以厚度5mm之耐熱玻璃被覆由 蔽），使液面變動抑制於0.5mm以下，且自該壓 突入水面之部位將累積於液面之十氫萘予以連 均一地冷卻，使該壓出溶解物質中之溶劑並不 解物質除去而以紡紗速度40m/min取回凝膠絲 並不將該凝膠纖維纏繞而在氮加熱烤爐烤爐中 輥乾燥該凝膠纖維中殘留溶劑濃度至7%爲止卷 / 拉伸比進行拉伸。所得聚乙烯纖維之諸物性如 (實施例3) 將極限黏度20.OdL/g之超高分子量聚乙烯與 量比1 0 : 90混合來形成漿液狀液體。將該物質 及運送部之2軸螺旋壓出機溶解，自所得透明 排列成圓形之孔數30個、直徑0.8mm之噴絲 壓出。將該壓出溶解物質，透過以構件被覆之 氣體介質空間，藉由通過以®定流之水所充滿 十氫蔡以重 合及運送部 的均一物質 _絲孔進行 件被覆之長 之水所充滿 外部空間遮 出溶解物質 續除去同時 自該壓出溶 狀。接著， ，使用驅動 t以8.8倍之 表1所示。 十氫萘以重 以具備混合 丨的均一物質 孔以1 . 8 g /分 長度 8 mm之 i之圓筒狀流 -21- 200909621 管（以厚度5 m m之耐熱玻璃被覆之外部空間所遮蔽）’使液 面變動抑制於0.5mm以下，且由該壓出溶解物質突入水面 之部位將累積於液面之十氫萘予以連續除去同時均一地冷 卻，使該壓出溶解物質中之溶劑並不自該壓出溶解物質除 去而以紡紗速度90m/min取回凝膠絲狀。接著，並不將該 凝膠纖維纏繞而在氮加熱烤爐中，以該凝膠纖維使溶劑乾 燥後以5.8倍之拉伸比進行拉伸。所得之聚乙烯纖維之諸 物性如表1所示。 (比較例1) 將極限黏度 19.6dL/g之超高分子量聚乙烯及十氫萘 90wt%之槳液狀混合物一邊分散一邊以設定成230°C溫度之 螺旋型捏合機溶解，使用輕量泵以單孔排出量1.6g/分供給 設定於175 °C之直徑0.6mm、具有400孔之紡嘴。使用設置 於噴嘴正下方之狹縫狀氣體供給噴絲孔注意使以1 · 2m/s高 速度調整於1 0 0 °C之氮氣體整流，儘可能使絲條以均等地接 觸之方式將纖維表面之十氫萘積極地蒸發，進而以設定於 1 1 5 °C之氮流將殘留於纖維之十氫萘蒸發’使用設置於噴嘴 下游之納爾遜式輥以80m/分之速度取回。此時’退火 (quench)區間之長度爲l.〇m’纖維之冷卻速度爲1〇〇 °C/s。 接著，將所得纖維在加熱烤爐下拉伸至4 · 0倍’接著在設 置此纖維之加熱烤爐中以4.1倍拉伸。在中途並不裂斷而 可獲得均一的纖維。所得聚乙烯纖維之諸物性如表1所示。 (比較例2) -22- 200909621 將極限黏度19.6dL/g之超高分子量聚乙烯分散於7wt%及 十氫萘93wt%之漿液狀混合物同時以設定於23CTC溫度之 螺旋型捏合機溶解，使用輕量泵以單孔排出量1 . 6g/分供給 於設定爲1 75 °C之直徑0.8mm、具有3 0孔之紡嘴。將該壓 出溶解物質，藉由1 〇mm之氣體介質空間，以水浴冷卻’ 使該壓出溶解物質中之溶劑並不自該壓出溶解物質除去而 以紡紗速度80m/分取回凝膠絲狀。接著，並不將該凝膠纖 維予以纏繞而是在氮加熱烤爐中，以3 · 0倍之拉伸比進行 拉伸。此時於4.5倍以上之拉伸比在烤爐中產生纖維之裂 斷。所得聚乙烯纖維之諸物性如表1所示。 (比較例3) 將極限黏度21.0dL/g、分子量分布Mw/Mn = 3.7之超高分 子量聚乙烯10wt%與十氫萘90wt%之漿液狀混合物供給於 設定爲230°C之螺旋型捏合機，予以溶解成爲紡紗液後，使 用170°C之紡紗嘴（孔徑0.7mm ’孔數400) ’進行以單孔排 出量1.4 g /分之紡紗。在紡紗絲，自設置於紡紗嘴正下方之 氣體供給用狹縫（slit)狀噴絲孔以平均風速Um/sec，將100 °C之氮氣儘可能的均等地吹上，將纖維表面之十氫萘積極 地蒸發，其後不久，以設定爲30°C之空氣流進行實質上冷 卻，藉由設置於紡紗嘴下游之納爾遜式輥（Nelson roUer)以 7 5 m/分之速度取回。此時，含於絲條之溶劑減少至原來重 量之約一半。接著，將所得絲條在100°C之加熱烤爐中拉伸 至4倍’進而在149。(：之加熱烤爐中拉伸至4倍’獲得聚乙 -23- 200909621 烯纖維。所得聚乙烯纖維之諸物性女 ]表1所示。 實施例1 實施例2 實施例3 比較例1 比較例2 總拉伸倍率Μ 11.0 8.8 5.8 16.4 3.0 纖度[dTex] 187 232 96 490 136 單纖維纖度[clTex] 6.2 7.7 3.2 1.2 4.4 強度[cN/dTex] 32.5 31.1 25.4 28.0 16.8 伸度[Ή 4.1 7.7 3.6 3.3 7.0 彈性率[cNdTex] 1085 1044 960 876 321 D8C面積比[-] 12.8:1.0 13.1:1.0 3.8:1.0 15.0:1.0 15.7:1.0 單絲長度方向之CV%[%] 12.0 11.4 8.7 28.9 30.8 單絲間之CV%[%] 11.5 13.8 12.2 25.2 28.8 拉伸步驟數[-] 1 1 1 2 1 [產業上之利用可能性] 本發明之高強度聚乙烯纖維因係高強度/高彈性率且纖 維內部構造爲均一的聚乙烯纖維，故各種運動衣料或防彈/ 防護衣料/防護手套或各種安全用品等之高性能紡織品、拔 河繩（tugrope) /繫船索/遊艇索/建築用繩等各種繩製品、釣 線、遮蔽纜線（b 1 i n d c a b 1 e)等各種絲編帶（b r a i d)製品、漁網 /檔球網等網製品進而有化學過濾器/電池隔版等補強材料 或各種不織布、帳棚等之布幕材料、或安全帽或滑雪板等 運動用或喇n八薄膜（speaker cone)用、或預浸材、混凝土補 強寺混合（composite)用之補強纖維等，在產業上可應用於 極廣範圍。 -24- 200909621 【圖式簡單說明】 【第1圖】表示羊肉串構造之模式圖。 【第2圖】顯示羊肉串構造之TEM照片。 【第3圖】中心部不具有羊肉串構造之纖維前驅物之TEM 照片。 【第4圖】表層不具有羊肉串構造之纖維前驅物TEM照 片。 【第5圖】具有實質上從中心至表層以羊肉串構造爲基 ί 本單位之微細構造爲其特徵之纖維前驅物之TEM照片。 【第6圖】適於本發明纖維之製造的拉伸步驟之模式圖。 【第7圖】習知拉伸步驟之模式圖。 【主要元件符號說明】 無0 -25-Further, the entire area of the endothermic peak indicates the area of the DSC curve and the portion surrounding the interpolating portion, and the area of the endothermic peak on the high temperature side indicates a temperature range of 150 degrees to 160 ° C (high temperature side). The peak of the DSC curve and the area surrounding the portion of the interpolated baseline. In this plastic transfer temperature determination method UIS K7121), the definition of peak 系 refers to the part of the DSC t curve that is detached from the baseline and returned to the baseline, but in the present invention, the obtained temperature-increasing DSC curve is differentiated only to differentiate the 値The situation from positive to negative is the peak. The method for producing the polyethylene fiber of the present invention is not particularly limited. However, in the fiber precursor having the above-described uniform kebab structure, it is desirable to increase the draw ratio in a state where the solvent concentration is lowered. When the solvent concentration is low and the film is stretched at a high magnification, the string structure (the disappearance of the mutton portion) can be effectively revealed by the present inventors. Specifically, it is exemplified that a driving roller is disposed between the fiber precursor take-up roller and the (one-stage) drawn wire take-back roller, and the speed of the relevant driving roller is adjusted between the fiber precursor take-up roller and the driving roller. A method of lowering the solvent concentration and increasing the draw ratio between the driving roll and the drawn wire winding roll. It is presumed that when the stretching is performed without providing a driving roller, the portion having a low viscosity, that is, the portion having a high solvent concentration is deformed, and it is difficult to form a string structure. Further, the stretching means can also achieve the effect that the stretching error between the filaments becomes small. That is, in the (first stage) stretching step, the solvent is stretched while evaporating, but in the case of the multifilament, the solvent is evaporated from the monofilament located on the surface of the bundle in the stretching zone, between the monofilaments. When the measurement of the solvent concentration is large, the stretching is performed in a state of -15 to 200909621. According to the above method, the solvent concentration difference between the monofilaments is reduced, so that the film is stretched at a high stretching ratio. The polyethylene fiber of the present invention is such that the monofilament is divided every 50 cm in the longitudinal direction, and the endothermic peak relative to the temperature rising DSC curve in the bound state of the divided single fiber, the heat absorption on the high temperature side The coefficient of variation (CV%) of the area of the peak area is preferably 22% or less. In the case of such a polyethylene fiber, in the case of a practical multifilament, the overall strength of the multifilament is determined depending on the portion having the smallest area ratio, and as a result, the strength of the multifilament becomes high, and on the one hand, the filament is broken or In the later step, the multifilament with less broken filaments. A better CV% is 17%, and particularly preferably 12% or less. The lower limit of CV% is not particularly limited, and even if it is less than 1%, the influence on strength and the like is hardly observed. In addition, CV% is defined by the following formula. CV% = l〇〇x standard deviation / average 値 (%) The means for obtaining such a polyethylene fiber is not particularly limited, and it is preferable to use the liquid as a cooling medium so that the liquid level fluctuation is as small as possible. As a result of the inventors' efforts, the high-strength polyethylene fibers having high productivity of the present invention are preferably obtained so that the liquid level fluctuation is 1.0 mm or less. When the liquid level fluctuates by more than 1.0 mm, the variation in the passage time of the gas medium space in the longitudinal direction of the monofilament and the monofilament becomes remarkable, and the structure of the monofilament significantly becomes uneven in the longitudinal direction and the filaments described later. In particular, in the case where the liquid level changes drastically, the monofilament is broken in the gas medium space. The polyethylene fiber of the present invention may be a multifilament, and the ratio of the endothermic peak of the DSC curve of the monofilament to the area of the endothermic peak of the high temperature side is between the filaments -16-200909621 coefficient of variation (CV % ) to 2 2% or less is preferred. More preferably, it is less than 7%, and particularly preferably less than 12%. The ratio of the ratio of the endothermic peak area ratio on the high temperature side is difficult to obtain high even if the average uniformity of the entire filament is worse than the monofilament between the monofilaments, the strength of the entire yarn depends on the monofilament having the smallest area ratio. Strength fiber. On the other hand, in the subsequent step, in the case of broken wires, it is also largely dependent on the monofilament having the largest area ratio. Therefore, by setting the c V % between the filaments of the multifilament within the above range, a multifilament having high strength and excellent post-processability can be obtained. The lower limit of the CV% between the filaments is not particularly limited, and even if it is lower than 1%, the effect is hardly changed. The method for producing the multifilament having a low C V % between the filaments is not particularly limited, but in the production of the fiber precursor, it is preferred to make the temperature of the atmosphere directly under the spinning nozzle uniform. As a result of the inventors' efforts, the ambient temperature difference between the filaments is ±3.0 ° C or less, preferably ±2.0 ° C or less, more preferably ± 1 · 〇 ° C or less, directly under the spinning nozzle. It is possible to make the difference in the structure between the filaments extremely small, and it is known that it is feasible to produce the high-strength polyethylene having high productivity of the present invention. Further, in the same place, the temperature difference of the elongating time is ±3.0 ° C or less, preferably ±2.0 ° C or less, more preferably ±1.0 ° C or less, so that the structural difference in the length direction of the monofilament can be made extremely small. The high-strength polyethylene of the present invention which can be produced is self-evident. Further, as described above, in the stretching step, a driving roller is provided between the fiber precursor take-up roller and the drawn wire take-up roller, and the adjustment of the driving roller speed can increase the stretching ratio in a state where the solvent concentration is low. It is preferred to make the stretching between the filaments uniform. -17- 200909621 In the range of the present inventors, the solvent concentration of the fiber precursor is preferably 30% or less when the driving roller passes. More preferably, it is 25% or less, and particularly preferably 20% or less. The polyethylene multifilament yarn of the present invention can be used to improve the productivity in comparison with the conventional one, and further exhibits a remarkable effect in the case of a fineness of 50.0 dtex to 100 tex dtex and a single yarn fineness of l_6 dtex to 250 dtex. That is, since the low draw ratio has a high strength and a high modulus of elasticity, the single yarn fineness can be increased, and since the measurement deviation between the filaments is small, it is high in the fineness of the high multifilament. For such a range of fineness and monofilament fineness, for example, in many applications such as fishing lines or gloves requiring rigidity or wear resistance, the performance can be improved. More preferably, the fineness is 130dtex~5 00dtex, the single-filament fineness is 2.0dtex~180dtex, the fineness is I50dtex~460dtex, and the single-filament fineness is 5.0dtex~130dtex. The average strength of the polyethylene multifilament in the present invention is preferably 25 cN/dtex or more, more preferably 27 cN/dtex or more. The average strength is less than 25 cN/dtex, and there is a possibility that the strength of the product is insufficient when the product is applied. [Embodiment] Hereinafter, the measurement method and measurement conditions of the characteristics 本 in the present invention will be described. (Extreme Viscosity) The specific viscosity of various dilute solutions is determined by the Ubbelohde capillary viscosity tube at 135 Torr. The least squares approximation is plotted against the concentration of the viscosity (-18-200909621). Least square approximation) The extrapolation point of the resulting line to the origin to determine the ultimate viscosity. At the time of measurement, the sample was divided or cut to make the sample a length of about 5 mm, and 1 wt% of an antioxidant (trade name "Yoshinox BHT", manufactured by Jifu Pharmaceutical Co., Ltd.) was added to the polymer, and dissolved at 135 ° C for 4 hours. To adjust the assay solution. (Strength, Tensileness, and Elasticity of Multifilament) In the present invention, the strength and the modulus of elasticity are "TENSILON" manufactured by Toray Scientific Co., Ltd., and the test piece has a length of 200 mm (length between chucks) and an elongation speed of 100%/min. The stress-strain curve is measured at an ambient temperature of 20 ° C and a relative humidity of 65%. The stress and elongation are calculated from the fracture point (cN/dtex), and the self-extension (%) is given. ), the maximum inclination of the wire near the origin of the curve is calculated by calculating the modulus of elasticity (cN/dtex). In addition, each 値 was used to measure the average enthalpy of 値 10 times. (Measurement of differential scanning calorimeter) The differential scanning calorimeter was measured using "DSC7 type" manufactured by Perkin Elmer. When the load of the denier (dtex) X 1/1 0 (g) is applied to the monofilament of 50 cm, it becomes a state in which the aluminum plate has no slack, and under inert gas, the temperature rises from room temperature at a temperature of 1 (TC / min). The temperature rise DSC curve was obtained at 200 ° C. After correcting the baseline of the obtained temperature rising DSC curve, the peak temperature was read, and the waveform separation process was performed to calculate the area of the entire endothermic peak ' and the area of the high temperature side endothermic peak , The ratio of the total area of the endothermic peak ' to the area of the endothermic peak of the 咼 temperature side is used. In the waveform separation system, the soft GRAMS/32 version 4 of the galactic industry company is used. In addition, the length between the monofilament and the monofilament is determined. 200909621 The ratio of the area ratio of the direction is such that the number of measured filaments is n = 20 ' in the state where the applied denier (dtex) X l/10 (g) is in the state of 50 cm of the monofilament' becomes a constraint on the slack of the aluminum plate. State, under the inert gas 'heating temperature from room temperature to 200 ° C at a temperature increase rate of 10 ° C / min ' to obtain a temperature rising DSC curve. After correcting the baseline of the obtained temperature rising DSC curve, read the peak temperature. Waveform separation processing, calculation of endothermic peaks値The body area 'and the endothermic peak area on the high temperature side, after obtaining the ratio of the total area of the endothermic peak of each monofilament to the endothermic peak area of the high temperature side, the CV % is obtained according to the following formula: f % CV% = 100X standard deviation / average enthalpy (%) (Example 1) An ultrahigh molecular weight polyethylene having an ultimate viscosity of 20.OdL/g and decalin was mixed at a weight ratio of 8:92 to form a slurry liquid. The two-axis screw extruder equipped with the mixing and conveying unit was dissolved, and the number of holes having a circular uniformity was 48, and the number of holes having a diameter of 〇·8 mm was pressed at 2.5 g/min. The molten material is extruded through a length of 8. mm, which is covered by the member, and the gas medium space is covered by a cylindrical flow tube filled with water of constant flow (covered by a heat-resistant glass covered with a thickness of 5 mm) "Reducing the liquid level fluctuation to 〇5 mm or less, and continuously removing the decahydronaphthalene accumulated in the liquid surface from the portion where the dissolved substance protrudes into the water surface, and uniformly cooling the solvent in the dissolved substance. Does not extract from the dissolved material, but at the spinning speed The gel filament was taken back at 30 m/min, and then 'the gel fiber was not entangled and dried in a nitrogen heating oven' using a driving roller to dry the residual solvent concentration in the gel fiber to 1%, 11 times. The draw ratio was -20-200909621. The physical properties of the obtained polyethylene fibers are shown in Table 1. (Example 2) The ultrahigh molecular weight polyethylene having an ultimate viscosity of 20. OdL/g was compared with the ratio of 1 0 : 90 The mixture was mixed to form a slurry liquid, and the material was dissolved by a two-axis screw extruder equipped with a mixture, and the number of holes which were transparently arranged into a circular shape was 30, and the diameter was 0.8 mm [2.5 g/min. The molten material was pushed out and passed through a gas medium space of a constitution of 10 mm, and the liquid level fluctuation was suppressed to 0.5 by passing through a cylindrical flow tube (covered with a heat-resistant glass having a thickness of 5 mm) of a constant flow k. Below mm, and the decahydronaphthalene accumulated in the liquid surface is uniformly cooled from the portion where the pressure is introduced into the water surface, so that the solvent in the dissolved substance is not removed, and is retrieved at a spinning speed of 40 m/min. The gel filaments were not wound and the film was dried in a nitrogen-heated oven oven to dry the gel fiber to a residual solvent concentration of 7% until the roll/stretch ratio was stretched. The physical properties of the obtained polyethylene fibers were as follows (Example 3) An ultrahigh molecular weight polyethylene having an ultimate viscosity of 20. OdL/g was mixed with an amount of 10:90 to form a slurry liquid. This material and the two-axis screw extruder of the conveying unit were dissolved, and the obtained number of holes having a circular number of holes of 30 and a diameter of 0.8 mm were extruded. The molten material is pushed out and passed through the gas medium space covered by the member, and is filled with water which is covered with a uniform substance _ wire hole which is filled with the water and filled with the water. The external space covers the dissolved material and continues to be removed from the solution. Next, the drive t is used to be 8.8 times as shown in Table 1. The decalin is weighted by a uniform material hole with a mixed enthalpy of 1. 8 g / min length 8 mm i of the cylindrical flow -21 - 200909621 tube (covered by a 5 mm thick heat-resistant glass-covered outer space) 'Inhibition of the liquid surface fluctuation to 0.5 mm or less, and the decahydronaphthalene accumulated in the liquid surface is continuously removed and uniformly cooled by the portion where the molten material is projected into the water surface, so that the solvent in the dissolved substance is not From the press-out of the dissolved material, the gel filament was taken back at a spinning speed of 90 m/min. Next, the gel fiber was not entangled in a nitrogen heating oven, and the gel fiber was dried with the gel fiber and then stretched at a draw ratio of 5.8 times. The physical properties of the obtained polyethylene fibers are shown in Table 1. (Comparative Example 1) A liquid-type mixture of an ultrahigh molecular weight polyethylene having an ultimate viscosity of 19.6 dL/g and a slurry of 90% by weight of decahydronaphthalene was dissolved while being dispersed at a temperature of 230 ° C, using a lightweight pump. A spinning nozzle having a diameter of 0.6 mm set at 175 ° C and having a diameter of 400 holes was supplied at a single hole discharge amount of 1.6 g/min. Use a slit-shaped gas disposed directly below the nozzle to supply the orifice. Note that the nitrogen gas is adjusted at a high speed of 1 · 2 m / s at 100 ° C to rectify the fiber as much as possible. The surface of the decalin was actively evaporated, and the decalin remaining in the fiber was evaporated by a nitrogen flow set at 1 15 ° C. The Nelson roller placed downstream of the nozzle was taken back at a rate of 80 m/min. At this time, the length of the 'quenching section' is l. 〇m', and the cooling rate of the fiber is 1 〇〇 ° C / s. Next, the obtained fiber was stretched to 4 × 0 times in a heating oven and then stretched by 4.1 times in a heating oven provided with this fiber. Uniform fibers are obtained without breaking in the middle. The physical properties of the obtained polyethylene fibers are shown in Table 1. (Comparative Example 2) -22- 200909621 An ultrahigh molecular weight polyethylene having an ultimate viscosity of 19.6 dL/g was dispersed in a slurry mixture of 7 wt% and decalin 93 wt% while being dissolved in a spiral kneader set at a temperature of 23 CTC. The lightweight pump was supplied at a discharge rate of 1.6 g per minute to a spinning nozzle having a diameter of 0.8 mm and having a diameter of 30 mm set at 1 75 °C. The molten material is pressed out and cooled in a water bath by a gas space of 1 〇 mm. The solvent in the molten material is not removed from the molten material, and the spinning speed is 80 m/min. Glue-like. Next, the gel fiber was not wound but stretched in a nitrogen heating oven at a draw ratio of 3.0 times. At this time, the draw ratio of 4.5 times or more causes cracking of the fibers in the oven. The physical properties of the obtained polyethylene fibers are shown in Table 1. (Comparative Example 3) A slurry mixture having an ultimate viscosity of 21.0 dL/g, a molecular weight distribution Mw/Mn = 3.7, an ultrahigh molecular weight polyethylene of 10% by weight, and a decahydronaphthalene 90% by weight was supplied to a spiral kneading machine set at 230 °C. After dissolving into a spinning solution, a spinning spun yarn having a single hole discharge amount of 1.4 g/min was used using a spinning nozzle (pore size: 0.7 mm 'hole number 400) of 170 °C. In the spinning yarn, nitrogen gas at 100 ° C is blown as evenly as possible from the slit-like orifice of the gas supply provided directly below the spinning nozzle at an average wind speed Um/sec. Decalin was actively evaporated, and shortly thereafter, it was substantially cooled with an air flow set at 30 ° C, and taken at a speed of 75 m/min by a Nelson roUer placed downstream of the spinning nozzle. return. At this time, the solvent contained in the yarn is reduced to about half of the original weight. Next, the obtained yarn was stretched to 4 times in a heating oven at 100 ° C and further at 149. (: stretching in a heating oven to 4 times 'to obtain polyethylene-23-200909621 olefin fibers. The physical properties of the obtained polyethylene fibers are shown in Table 1. Example 1 Example 2 Example 3 Comparative Example 1 Comparison Example 2 Total draw ratio Μ 11.0 8.8 5.8 16.4 3.0 Fineness [dTex] 187 232 96 490 136 Single fiber fineness [clTex] 6.2 7.7 3.2 1.2 4.4 Strength [cN/dTex] 32.5 31.1 25.4 28.0 16.8 Extension [Ή 4.1 7.7 3.6 3.3 7.0 Elasticity [cNdTex] 1085 1044 960 876 321 D8C area ratio [-] 12.8:1.0 13.1:1.0 3.8:1.0 15.0:1.0 15.7:1.0 CV% of the length of the monofilament [%] 12.0 11.4 8.7 28.9 30.8 Monofilament CV% [%] 11.5 13.8 12.2 25.2 28.8 Number of stretching steps [-] 1 1 1 2 1 [Industrial use possibility] The high-strength polyethylene fiber of the present invention is high in strength/high modulus and fiber The internal structure is a uniform polyethylene fiber, so various sports fabrics or bulletproof / protective clothing / protective gloves or various safety products such as high-performance textiles, tug-of-war ropes / tufts / yacht ropes / construction ropes, etc. Various silk braids such as products, fishing lines, and shelter cables (b 1 indcab 1 e) Braid products, fishing nets, nets and other net products, such as chemical filters/battery partitions and other reinforcing materials or various non-woven fabrics, tents, etc., or sports helmets or skis, etc. Speaker cone), or prepreg, reinforcing fiber for concrete reinforcement, etc., can be applied to a wide range of industries. -24- 200909621 [Simple diagram] [Fig. 1] shows lamb Schematic diagram of the string structure. [Fig. 2] shows the TEM photograph of the mutton string structure. [Fig. 3] TEM photograph of the fiber precursor without the kebab structure at the center. [Fig. 4] The surface layer does not have the mutton string structure. TEM photograph of the fiber precursor. [Fig. 5] TEM photograph of a fiber precursor characterized by a fine structure of the unit from the center to the surface layer. [Fig. 6] Schematic diagram of the stretching step for the manufacture of the inventive fiber. [Fig. 7] Schematic diagram of the conventional stretching step. [Main component symbol description] No 0 - 25-