472090 A7 B7 五、發明說明（ 域 領 術d- 運 r 機 飛 於 適 束 維 纖 糸 腈 烯 丙 <ί 1 種1 於 I- 係 明 發 本 造 製 之 絲 維 纖 碳 用 所 途 用 業 產 般1 及 M 途 一 用術 化枝 強景 等背 化前 強目 等。 動展 運進 、 有 機大 飛面 在方 , 等 增途 曰用 要業 需產 的般 絲一 維等 纖築 碳建 來木 年土 幾、 近途 用 腈單 烯的 丙維 的纖 00碳 ,0此 20將 Ϊ , 00絲 o’維 AW. .,*-/< 1 纖 在碳 數成 絲製 细驟 取步 捲燒 法烺 繞經 捲 ， 絲束 细維 K 纖 是糸 絲 維 纖 碳 到 得 驟 步 燒 煆 過 經 於 。 由 型 ， 成中 Μ 法 加方 ，述 齊上 拉在 支是 數可 絲 間彈 之或 此度 彼強 維體 纖型 碳成 勺 齊維 拉纖 在碳 , 用 齊使 拉生 支產 數會 絲時 維型 纖成 碳 ， 將隙 要間 ，生 後易 齊因 拉肇 支之 數昂 絲高 維本 纖成 碳和 用雜 採煩 ，續 外手 此時 。 作 陷製 缺品 MW uy 相成 之為 低成 降 ， 數驟 係步 性的 的 禮 15i 前 絲 維 纖 碳 加 增 試 嘗 來 年。 近數 ，絲 題細 問束 等維 此纖 決糸 解腈 為烯 丙 束法 絲無 及 ， 涉大 會加 ，荷 束負 絲燥 细乾 L、J 勺 束置 維裝 纖有 糸現 腈 ， 烯加 丙增 加量 增容 亂束 ，絲 是和 可運 搬 (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 纖 生 發 會 也 〇 ，低 加降 增著 量顯 易質 容品 束品 絲製 因致 -Μ 外 ， 另題 。 問 度限 速極 絲的 纺間 高束 提維 必 1 0 束小 維性 纖束 系集 腈且 烯 ， 丙小 的荷 體負 驅燥 前乾 絲 ， 維優 纖性 碳密 做緻 用 ， 適大 , 度 此織 因總 須 絲燥 維乾 纖 ， 碳優 做性 用密 適緻 -WTH1 種 ， 一 大 供度 提纖 於總 在 ， ，束 的維 目纖 之糸 明腈 發烯 本丙 , 的 Μ 體 所驅 前 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 製 之 束 維 纖 糸 腈 烯 丙 ——1 種 一 供 提 。 於 小在 性， 束的 集目 且一 而另 , 明 小發 荷.本 負· 束 集。 且束 隹 1 小纖 荷糸 負腈 燥烯 乾丙 ，之 優體 性驅 密前 緻絲 因維 得纖 可碳 實做 確用 並適 易而 容 ， , 優 法性 沭 概 明 發 決 解 法 製 其 及 束 維 纖 系 腈 烯 丙 明 發 本 用 利 可 題 課 述 上 束成 維製 纖所 糸物 腈合 烯聚 丙腈 用烯 體丙 驅之 前位 維單 纖腈 碳烯 種丙 一 上 於 Μ 關 % 係 量 明重 發95 本含 即 由 單 ~ 之 的 5 量 束 G 重 維度束 纖高維 該而纖 成續該 構連為 , 上 量 為質碘 徵實吸 特有且 其向 ， ,縱在 上的存 Μ束個 ο 隹 5 AW 11 ο,纖一 ο 令 2 3 方 在 ， 數面 旦表 總維 ，纖 紋 縐 的 特 法 製 之 束 維 纖 糸 腈 烯 丙 用 澧 區 前 。 維 者纖 % 碳 量明 重發 5本 I又 物腈溫 合烯 ， 聚丙 ％ 系將量 腈有重 烯含70 丙於 ~ 的出50 位壓度 單 ，濃 腈液劑 烯原溶 丙絲機 上纺有 Μ得二 &€ 所第 量劑得 重溶所 95機解 含有溶 將一物 , 第合 為於聚 徵溶系 成下 ， ,Μ 綠 中倍固 液 8 凝 .固 〇 此 凝速將 一 線再 第出 ， 的壓拉 成液抽 組原中 液絲液 溶纺固 水 Μ 凝 劑絲一 溶固第 機凝該 有此從 的將 ， 0C , 度 50絲速 ~ 固拉 30凝抽 度為之 -n n H ϋ ϋ ϋ ϋ ϋ n n I ^ n n (請先閱讀背面之注意事項再填寫本頁) I . .線. 經濟部智慧財產局員工消費合作社印製 LO 第 度的 濃成 劑組 溶液 機溶 有水 三劑 第溶 得機 所有 解的 溶 υ 物 5 合 ~ 聚30 糸 度 Μ^ 烯 ， 丙 ％ 將量 有重 i ο 含 7 於 ~ 第束 於維 ，纖 中潤 法膨 製之 束前 。 維燥 伸纖乾 延糸後 倍腈伸 α烯延 -3丙倍 1明ο 1.發~3 Κ本 1 施的1. ，成施 中構實 液述中 固上液 凝在固 二 凝 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 Α7 Β7 3 ^_ 經濟部智慧財產局員工消費合作社印製 發明說明（） 宜令膨潤度在70重量3!以下。第二凝固液中的延伸倍數 太大時，會使後延伸的延伸倍數減少。 (請先閱讀背面之注意事項再填寫本頁) 再者，本發明磺纖雄前驅體用丙烯腈糸纖維束之製法 另一待歡為，將含95重量％以上丙烯腈單位的丙烯腈条 聚合物溶於第一有機溶劑所得纺絲原液，壓出於含有將 丙烯腈糸聚合物溶解所得第二有機溶劑濃度50〜70重量％ ，溫度3 0〜5 0Ό的有機溶劑水溶液組成的第一凝固液中 ，成為凝固絲，將此凝固絲以紡絲原液壓出線速0.8倍 以下之抽拉速度，從該第一凝固液中抽拉，再將此凝固 絲，於含有將丙烯腈条聚合物溶解所得第三有機溶劑濃 度5G〜70重量％,溫度30〜50°C的有機溶劑水溶液組成 的第二凝固液中，施以1.1〜3.0倍延伸，然後再進行4 倍以上濕熱延伸。 在上述構成的本發明丙烯腈糸纖維束製法中，施以濕 熱延伸後乾燥前的膨潤纖維束，以膨潤度在70重量以 下為佳。 在本發明丙烯腈糸纖維束及其製法中，丙烯腈条聚合 物僳使用含丙烯腈95重量SS以上之聚合物β此丙烯腈糸 聚合物可用丙烯腈均聚物或共聚物，或此等聚合物之混 合物。 丙烯腈共聚物偽丙烯腈共聚性單體與丙烯腈之共聚合 生成物，丙烯腈共聚性單體有（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁 酯、（甲基）丙烯酸己酯等（甲基）丙烯酸酯類，氣乙烯、 -5-本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 κι _Β7_ 五、發明說明（） (請先閱讀背面之注音？事項再填寫本頁) 溴乙烯、氣亞乙烯等鹵化乙烯類、（甲基）丙烯酸、衣康 酸、丁烯酸等具有聚合性雙鍵之酸類及其鹽類，馬來醯 亞胺、苯基馬來醯亞胺、（甲基）丙烯醯胺、苯乙烯、《 -甲基苯乙烯、乙酸乙烯酯，以及苯乙烯磺酸鈉、烯丙 基磺酸納、办-苯乙烯磺酸納、甲基烯丙基磺酸鈉等含 磺基之聚合性不飽和單體、2 -乙烯基吡啶、2 -甲基- 5-乙烯基毗啶等含吡啶基之聚合性不飽和單體時，惟不限 於此。 聚合方法有例如水溶液内的氣化還原聚合，非均質条 中的懸浮聚合，使用分散劑的乳化聚合等，惟不限於此。 本發明碳纖維前驅體用丙烯腈条纖維束，傺總旦數在 30, 000(33,OOOdtex)以上的纖維束，在形成纖維束的單 纖維表面，於纖維束縱向具有實質上連續而高度0.5〜 1.0# m的縐紋2〜15锢。本發明在不特定選擇的纖雒表 面ΙΟ^ιπΧΙΟαβ範圍，於連績縱向具有可觀察得到的凸 部，於此以規定的「縐紋」加以定義，計數其値數。 由於有此縐紋存在，本發明丙烯腈糸纖維束具體良好 的集束性，且以該纖維束為前驅體之碩纖維，用於製造 經濟部智慧財產局員工消費合作社印製 靜因前纖 生 ，為開 發時束的 易低維好 容太纖良 ,度該得 加高以可 增紋於 ， 積縐由際 面而及之 。表 以物 性的低，浸 纖束降性預 開維性束造 的纖束集製 好，集好在 良時的良 ， 示高束的絲 顯太維帶維 ，度纖附纖 時高使在磺 物紋會存之 浸缁，紋體.。 預電縐驅性 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（5) 因此，縐紋的高度Μ 0 . 6〜0 . 8 w m為佳。就縐紋寬度 言，在0.5〜l.Owm左右，以0.6~0.8/^1«為佳。 (請先閱讀背面之注意事項再填寫本頁) 前述縐紋個數太多時，纖維束表面積增加，易發生靜 電，致使纖維束的集束性降低。而此縐紋個數太少時， 因縐紋存在附帶的良好集束性，Μ及由於以該纖維束為 前驅體之碳纖維絲，在製造預浸物之際，可得良好之開 纖性。 因此，在構成本發明纖維束的單纖維束表面，必須有 縐紋2〜1 5個，Μ 1 2〜1 5個為佳。另外，本發明所規定 縐紋個數，並非構成纖維束的所有單纖維都一定要有此 數量的趨紋，有80% Μ上，K 90¾ Μ上為佳，更好是有 95¾ Μ上的單纖維有此數目的謅紋即可。 再者，本發明纖維束，每單位纖維重量的吸碘量必須 為0.5-1.5重量％ , Μ0.5-1.0重量％為佳。此吸碘量為 丙烯腈系纖維束緻密度的衡量，按特開昭6 3 - 8 5 1 6 8號公 報所載，依照下列吸碘法測得之值。 吸碘畺夕測最方法 經濟部智慧財產局員工消費合作社印製 精密秤取纖維長度5 - 7 c m的乾燥試料約0 . 5克，放入 附設共柱的2 0 0毫升三角燒瓶内，加碘液（秤取I 2 5 1克， 2,4 -二氯酚10克，乙酸90克，碘化鉀100克，移至1公 升量筒，用水溶解成定量1公升的碘液）1〇〇毫升，在 6 0 ± 5 °C振搖5 0分鐘，進行吸收處理後，令吸碘的試料 在流水中洗灌3 0分鐘，再進行離心分離之（2 0 0 0 r p m X 1 分鐘），盡使風乾，精確秤量，求出重量增加。 -7-本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7_ 五、發明說明（） <請先閱讀背面之注咅？事項再填寫本頁) 纖維束吸碘量值太小時，表示纖維束緻密度太高，即 纖維表面緻密度高，纖維表面的形態平滑，不宜。另方 面，纖維束吸碘量值太大時，表示纖維表面的緻密度太 低。如此一來，製得丙烯腈糸纖維束時的乾燥負荷大， 問題是無法提高紡絲速度。而且煅燒所得磺纖維絲的強 度太低。 本發明丙烯腈糸纖維束由上述構成，卽使總旦數在 30,000(總纖度33, OOOdtex)以上之任何絲束，均具有良 好的集束性，而且可由該纖維束進行髙密度煅燒。因此 ，可進行高密度锻燒之本發明效果，以總纖度55, 000 dtex以上之纖維束最為有效。 此外，本發明纖維束，按下述測量方法測得之靜電帶 電量在- lkV〜+ lkV範圍時，有利於提高纖維束的集束性 。尤其是此靜電帶電量在-5 k V〜+ 0 . 5 k V範圍時，由於纖 維束的延伸，單纖維的損壞少，不會附帶降低性能，可 保持安定的高品質。 靜雷错雷畺夕測眚方法 表面實施硬鍍鉻的2台鐵製二夾棍，設在彼此分開60公尺 ,測量對象的丙烯腈条纖維束經過此夾棍間，於捲取測 經濟部智慧財產局員工消費合作社印製 ο 量時 ir測變 a 始不。 S 。 開.壓量 品分 ，電電 製公進帶帶 司 5 行 ，電 公 =5 Π 定靜 電束ni穩之 靜維B/進束 ldo纖50行維 hi糸以束纖 is腈束維糸 sh烯雒纖腈 置丙纖条烯 設離糸腈丙 ，，腈烯為 處部烯丙即 分一丙該， 公器令俟值 10測，，壓 前探次壓電 棍之其電帶 夾III帶之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 經濟部智慧財產局員工消費合作社印製 維油等 ，度 製 束糸溶 ％固 此劑液 一聚解 ，液 8 纖的劑性強 之 維腈有量凝速令溶溶 另糸溶 ％固0 該時油束高 束 纖烯含重一線次機水 束腈有量凝速 在此糸集提 維 系丙於70第出其有劑。維烯含重一線 便。酯之有 纖 腈的出 ~ 之壓，三溶伸纖丙於70第出 Μ 性族束， 系 烯位壓50成液拉第機延糸的出 ~ 之壓 ，束脂維絲 腈 丙單 ，度組原抽得有的腈位壓50成液 劑集硫纖維 烯 用腈液濃所絲液所的倍烯單，度組原 油高含糸纖 丙 體烯原劑液纺固物 ρϋ 丙腈液濃所絲 予提、腈碳 用 驅丙絲溶溶以凝合50-3用烯原劑液纺 賦步劑烯得 體 前上纺機水絲一聚~1~體丙絲溶溶以 可一油丙所 驅 維 Κ 得有劑固第糸301.驅上纺機水絲 還進系高燒 前 纖 ％ 所二溶凝該腈在施前 Μ 得有劑固 束，酯提煆 維 碳量劑第機此從烯度實維 ％ 所二溶凝 維内族但束 纖 明重溶得有令度丙溫，纖量劑第機此 纖圍芳不維 碳 發95機所的，速解，中碳重溶得有令 系範、劑纖 明 本有有物°0絲拉溶 ％.液明95機所的 , 腈當劑油系。發 在含一合50固抽有量固發有有物 Ρ 絲 烯適油糸腈用本。 ，令第聚 ~ 凝之含重凝本含一合50固 丙值糸酮烯作就明述，於糸30為下在70二在令第聚 ~凝 明壓酮矽丙的，說所中溶腈在成 Μ ，~第’，於糸30為 發電矽，該率次 Μ 前法物烯度，倍絲50之外中溶腈在成 本帶有又對性其加如製合丙溫中 8 固度成此法物烯度 ， '束劑〃且彈 法 之聚解，液 ο 凝濃組 製合丙溫中 ------------->衣·。-------訂·-------I (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7_ 五、發明說明（） (請先閱讀背面之注意事項再填寫本頁) 倍以下之抽拉速度從該第一凝固液抽拉，其次令此凝固 絲，在含有溶解丙烯腈糸聚合物所得第三有機溶劑濃度 50〜7G重量％ ,溫度在30〜50°C的有機溶劑水溶液組成 之第二凝固液中，實施1.1〜3.0倍的延伸，然後進行4 倍以上之濕熱延伸。 本發明所用第一至第三有機溶劑，均為可溶解丙烯腈 条聚合物之有機溶劑，有例如二甲基乙醯胺、二甲亞硯 、二甲基甲醯胺等。 紡絲原液可用丙烯腈条聚合物溶於第一有機溶劑所得 之有機溶劑溶液。第一有機溶劑尤以二甲基乙醯胺為 佳《不但具有不因溶劑加水分解致使紡絲原液性能惡化 的良好紡絲性之紡絲原液，而且在丙烯腈糸纖維束煅燒 後，可得性能安定的碩纖維。 壓出紡絲原液所用紡嘴，可以採用丙烯腈条纖維束在 紡絲時，具有製造一般粗度在l.Qdtex左右的丙烯單纖 維所用孔徑，即15〜100# m孔徑的噴孔之纺嘴。尤其是 ，由於「凝固絲抽拉速度/紡絲原液從噴嘴壓出的線速 度」在0.8以下，可維持良好的紡絲性之關係，以使用 具有1 5〜5 0 a b孔徑的噴孔之紡嘴尤佳。 經濟部智慧財產局員工消費合作社印製 另外，本發明所規定第一凝固液和第二凝固液之條件 ，以及在第二凝固液中的延伸條件，對提高所得丙烯腈 条纖維束的定向具有重要性。 第一凝固液中的第二有機溶劑濃度，和第二凝固液中 的第三有機溶劑濃度，均為前述之50〜70重量χ ，為使 -1 0 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 經濟部智慧財產局員工消費合作社印製 實度 有溫 機， 的最 含劑於二 了出無 氣段度 度濃 亦的 有外 中， 所溶由第 為壓則 空手溫 濃劑 ，液 三固 液劑 絲機。著 ，的小 在伸制 劑溶 同固 第凝 固溶 固有態接 述液太 可延控 溶機。相凝 至勻.凝機 凝中狀使 後原， 亦之易 機有佳約二 一均 一有 該液固， 如絲佳 ，中容 有的 W 大第 第絲 第三 於固凝絲 ，紡為 絲液中 的中内度和 是固 ，第 由凝半固 度使下。固固驟 中液以溫液。其凝 劑的 ，一成凝 速在M上凝凝步 液固 ％ 液固佳尤除 溶中 絲第固出 的點倍 Μ 之二伸 固凝量固凝為，， 機液 固該凝抽 絲重 5 倍態第延 凝二重凝一内同來 有固 凝過面中 固其 03 狀在在 二 ，3 二第以相一 一凝 的超表液 凝 ，ΜΟ 脹述而 使言 Μ 第。Ρ.宜此 第二。出 ，的固。拉固尤在膨上 ， ，而，和固i3類如 用第胺抽度絲凝好抽凝。般般用固 固體内液凝 D 種。 所及藤液濃固一良中勻下一原採凝 凝具 Μ 固勻、 劑佳。液 Μ 乙固劑凝第性液均 Μ ，的絲之 句。％ 凝均1¾溶為劑原，基凝溶在從伸固中倍固液固絲 均佳量一的 i 機同溶絲劑甲一機只，延凝液 〇〇 凝固凝固 行為重第絲ci>有相收纺溶二第有故態的 一固 ο 匀凝此凝 進同 5 ，固5T，類回，機用從的，狀中第凝在均有，進 絲相在者凝在外種易此有使，中度等液該一度成含伸促 固，上差再於差此劑容因二都又體濃此固從第速形在延可 凝，質相 .益度 溶還 第好 液之在凝 在線法 中， (請先閱讀背面之注咅？事項再填寫本I) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 10 經濟部智慧財產局員工消費合作社印製 時維發倍纖 Μ 此 ， 束而二伸 於容在烯 Μ 接顯熱 行纖會 1 糸 ，因 束 維 ，第延 可會度丙，伸明濕 進單中 1 腈 時， 維 纖燥將中 ，，纖明伸延驟此 倍生液在烯 驟佳 纖 之乾：洗 束驟總發延中步在 3 .發固率丙 步為. 之 態以有水 維步得本的液伸。 數易凝倍到 伸行 態。狀加法在。纖之製之後固延束 倍容二伸得 延進 狀束脹，'方，性之伸欲象驟凝著維 伸，第延而 熱下 脹維膨後之束產態延故對步二隨纖 延中在而伸 濕 Μ 膨纖的向伸維生狀以，為伸第會糸 過驟，。延 取倍。的糸後定延纖高潤加低束延在不腈 超步時絲中 採 ο 性後腈成維熱之提膨後降維中即，烯 伸伸行纺液 再 2 伸伸烯完纖濕態 Μ 圼燥顯纖液亦時丙 延延進法固 ，的延延丙伸高。狀伸而乾明系固。伸的 綠熱倍無凝 後數的中之延提束脹延成取性睛凝佳延化 固濕 4 ，二 伸倍驟液的中步維膨中完採束烯二為熱密 凝等過毛第 延伸步固標液一纖圼水伸惟集丙第法濕緻 的伸超起在。中延伸凝得固進系束沸延，致的在方的得 中延而或因果液中延二 ，凝 Μ 腈結或中伸 Κ 上 ，之上而 液水。裂難效固液热第燥二伸烯伸中液延 ，Μ 時伸Μ, 固沸毛斷很向凝固濕在乾第延丙延水固 Μ 電ex束延倍性 凝在起維，定二凝在，經將熱之中熱凝加靜dt維熱 4 束 二如或纖時之第二高次後可濕的液在二後生00纖濕行集 第。例裂單下束在第提其洗亦在標固或第燥發,0糸用進低 _ ，斷生 Μ 維 在可 水 ，得凝 ， 乾易33腈採著降 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 11 五、發明說明（） 延伸之延伸倍數，可適當決定，例如8倍以下。 (請先閱讀背面之注意事項再填寫本頁) 再者，在本發明製法中，實施延伸後乾燥前的膨脹纖 雒束之膨潤度在70重量ί:以下，以該纖維束為前驅體的 磺纖維絲成為髙性能碩纖維絲之點為佳，由於在第一凝 固液中製造凝固絲之際，降低「凝固絲抽拉速度/纺絲 原液從噴嘴壓出的線速度」，使第一凝固液中的凝固絲 可均勻凝固，接著在第二凝固液中延伸時，成為均勻定 向到内部為止之絲條，即可使實施延伸後乾燥前的膨脹 纖維束之膨潤度在70重量％以下。 即，在第一凝液中製造凝固絲之際，若提高「凝固絲 抽拉速度/紡絲原液從噴嘴壓出之線速度」時，該第一 凝固液中的凝固絲同時發生凝固和延伸，會使第一凝固 液中凝固絲的凝固不均勻。因此，即使在第二凝固液中 延伸，實施延伸後乾燥前的膨潤纖維束之膨潤度低，即 無法形成均勻定向到内部為止之絲條。 然而，乾燥前呈膨潤狀態的纖維束之膨潤度，傺設離 心分離機（30GGrpm， 15分鐘）除去呈膨潤狀態的纖維束 吸附液後之重量為W ,以1 1 Q°C熱風乾燥機乾燥2小時 後之重量為W 0 ,則由下式求出的數值即是： 經濟部智慧財產局員工消費合作社印製 膨潤度 U) = (W-W0)X/W0 本發明製法中，於第二凝固液中進行延伸後，或於第 二凝固液中延伸後接箸進行濕熱延伸後之纖維束，利用 公知乾燥方法加以乾燥，即可得標的之丙烯腈条纖維束。 又因本發明丙烯腈条纖維束緻密，可得高度生産性， -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7_ 五、發明說明（） (請先閱讀背面之注咅 ？事項再填寫本頁) 故不但使用上述高性能磺纖雒用前驅體可得高強度，産生 具有丙烯腈糸纖維之耐藥品性，而且可就此做為短切纖 維，在産業材料中用做補強纖維。 太發明慕佳啻旆形能 玆根據實施例説明本發明丙烯腈条纖維束及其製法之 具體構成。 在實施例中，縐紋之觀察是使用表面掃描型電子顯撤 鏡，以高倍數觀察纖維表面形態，在不特定選擇的纖維 表面1G 乂 mxi0；um範圍，計數在縱向連續觀察得到的缁 紋。 奮施例1 取丙烯腈、丙烯酸甲酯、異丁烯酸、使用過硫酸銨-亞硫酸氫銨、硫酸鐵，利用水糸懸浮聚合法共聚合，得 丙烯腈單位/丙烯酸甲酯單位/異丁烯酸單位=9 5/ 4/1 (重量）構成之丙烯睛条共聚物。將該共聚物溶於二甲基 乙醯胺，調製成濃度21重量％之紡絲原液。 此紡絲原液通過孔數5 0 , 0 0 0、孔徑6 0 # m的紡嘴，壓 經濟部智慧財產局員工消費合作社印製 構液拉甲倍 液原抽二 2 伸 溶絲中的 1·延 水紡液 ％ 伸中 胺以固量延水 醯絲凝重中沸 乙固一65液於 基凝第度在再 甲此該濃 ，， 二 ，從，液倍 的絲度 P 固 0 X 固速 3 凝 2 量凝拉度二伸 重為抽溫第延 65成倍至之時 度，4 引成同 濃中0.導組 ， ，液之著液洗 P 固度接溶水 35凝速絲水行 度一線固胺進。 溫第的凝醯次倍 於之出此乙其 5 出成壓 C 基 C2. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 13 後1C 理 1 處度 劑強 油-維 -纖472090 A7 B7 V. Description of the invention (Domain Collar d-R aircraft flying on a suitable bundle of fiber-glass fiber nitrile allyl < ί 1 type 1 in I- series Mingfa Ben made silk fiber carbon The industry-like 1 and M are used to transform the strength of the branches before the transformation of the eyes, etc. Moving exhibitions, organic large flying noodles are on the side, and so on. The carbon fiber is carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, carbon fiber, and carbon fiber. The method of making small steps is to wind the warp with a step-by-step method, and the tow K-fiber is made of carbon fiber. The step-by-step method is too strong. The branch is the number of filaments that can be struck or at this time the strong dimensional fiber type carbon into a spoon of Qiweila fiber on the carbon. Use the Qi to pull the number of silk to produce the number of silk fiber into the carbon, the gap should be between, after birth Yi Qi's number of Angstrom high-dimensional fibers formed by La Zhaozhi and carbon fiber are annoying, and continue to be used at this time. Low yield, the number of steps is stepwise before the 15th year of silk fiber carbon addition test to try the next year. Recently, the silk question asked the beam and other dimensions this fiber must not solve the nitrile solution than the allyl fiber method, Involved in the general assembly, the bundled negative wire is dry and dry. The bundled fiber is provided with nitrile, and the acrylic resin is added to increase the volume and disorder. The silk is and transportable (please read the note on the back? Matters? (Fill in this page) The Printing and Hair Development Conference of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs also reduced the increase and decreased the volume and the quality of the product. 10 high-strength spinning fiber bundles of small-dimensional fiber bundles are nitrile and ene, and the small acrylic carrier is negatively driven to dry the pre-dried filaments. Because the fiber must be dry and dry, and the carbon has good workability, it is a kind of dense-WTH1. It has a large supply of fiber to the total fiber. The paper size before driving is applicable to China National Standard (CNS) A4 (210 X 297 male) (%) 472090 A7 B7 V. Description of the invention (Bundled fiber cellulose nitrile allyl—one kind for one supply. For the small nature, the collection of the bundle and the other, Ming Xiaofa. The negative · bundle set. And the bundle of 1 small fiber loaded with negative nitrile drying allyl acrylic, the excellent physical properties before the compaction of the silk due to vitamin fiber can be practical and easy-to-use. Preparation of the fiber and the fiber-based nitrile allyl Mingfa with a Leica title on the fiber-based fiber preparation of nitrile propylene polyacrylonitrile using propene to drive the pre-dimensional monocellulose carbene propylene allyl In Μguan%, the amount of retransmission is 95, which consists of a single beam of 5 beams, a beam of G dimensions, a beam of high dimensions, and a fiber that continues to form the structure. The upper amount is specific to the absorption of quality iodine and its direction,纵 5 AW 11 ο, fiber one ο let 2 3 square, the total dimension in several planes, the special fiber bundle made of fiber texture crepe fiber acrylic nitrile allyl area . The content of carbon fiber is 5%, the content of carbon is 5%, and the content of nitrile is melamine. Polypropylene% is the content of nitrile with 70% propylene and 50% pressure. The concentrated nitrile solution is olefin-soluble propylene silk. The machine is spun with M and II. The amount of the solution is reconstituted. The 95 solution is dissolved in the solution, and the solution is combined under the polymer solution system. The green solid solution 8 is solidified. The coagulation speed will be the first line, and the pressure will be drawn into the original draw liquid group. The original silk will be dissolved in the spinning solution. The coagulant will be solidified and the machine should be solidified. 30 Condensation pumping degree is -nn H ϋ ϋ ϋ ϋ ϋ nn I ^ nn (Please read the precautions on the back before filling out this page) I... Concentrated agent group solution is dissolved with water in three doses. The dissolved solution is dissolved in the solution. The solution is 5 ~~ 30 mol, and the percentage is heavy. Ο Contains 7 to ~. Before the run of Zhongrun expansion method. After the drying of the fiber and the extension of the fiber, the acetonitrile is extended to 3 propenes, and the ratio is 1 to 1. The hair is made from 3 to 3 K. This is 1. The solution is solid and the liquid is solidified on the solid. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 472090 Α7 Β7 3 ^ _ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives printed the invention description () The swelling degree should be less than 70 weight 3 !. When the extension ratio in the second coagulation liquid is too large, the extension ratio of the rear extension is reduced. (Please read the precautions on the back before filling this page.) Furthermore, another method for preparing the acrylonitrile / fiber bundle for the sulfonated male precursor of the present invention is to add an acrylonitrile strip containing more than 95% by weight of acrylonitrile units. The spinning dope obtained by dissolving the polymer in the first organic solvent is pressed to a first solution containing an organic solvent aqueous solution having a concentration of 50 to 70% by weight of a second organic solvent obtained by dissolving the acrylonitrile polymer and a temperature of 30 to 50 ° C. The coagulated liquid becomes coagulated silk, and the coagulated silk is drawn from the first coagulated liquid at a drawing speed of 0.8 times or less the spinning original hydraulic output wire speed, and the coagulated silk is then mixed with an acrylonitrile strip. In the second coagulation solution composed of an organic solvent aqueous solution having a concentration of 5G to 70% by weight of the third organic solvent and a temperature of 30 to 50 ° C, the polymer was dissolved, and the extension was applied to a range of 1.1 to 3.0 times, and then the wet heat extension was performed 4 times or more. In the method for producing an acrylonitrile rayon fiber bundle of the present invention having the above-mentioned configuration, it is preferable that the swelling fiber bundle before drying is applied after moist heat stretching, and the swelling degree is preferably 70 weight or less. In the acrylonitrile 糸 fiber bundle and the preparation method thereof according to the present invention, acrylonitrile polymer 条 uses a polymer containing acrylonitrile with a weight of 95 SS or more β. The acrylonitrile 糸 polymer may be an acrylonitrile homopolymer or copolymer, or the like A mixture of polymers. Copolymerization product of acrylonitrile copolymer pseudo-acrylonitrile copolymerizable monomer and acrylonitrile. Acrylonitrile copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , (Meth) acrylic acid esters such as butyl (meth) acrylate, hexyl (meth) acrylate, gas vinyl, etc. -5- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 472090 κι _Β7_ V. Description of the invention () (Please read the note on the back? Matters before filling out this page) Vinyl halide, such as ethylene bromide, vinylidene, (meth) acrylic acid, itaconic acid, butyronic acid, etc. have polymerization Of acidic double bonds and their salts, maleimide, phenylmaleimide, (meth) acrylamidine, styrene, -methylstyrene, vinyl acetate, and styrenesulfonic acid Sulfur-containing polymerizable unsaturated monomers such as sodium, sodium allyl sulfonate, sodium-styrene sulfonate, sodium methallyl sulfonate, 2-vinylpyridine, 2-methyl-5 -When it is a pyridyl group-containing polymerizable unsaturated monomer such as vinylpyridine, it is not limited thereto. The polymerization method includes, for example, gasification reduction polymerization in an aqueous solution, suspension polymerization in a heterogeneous strip, emulsion polymerization using a dispersant, and the like, but is not limited thereto. The acrylonitrile strip fiber bundle for the carbon fiber precursor of the present invention has a fiber bundle with a total denier of 30,000 (33,000 dtex) or more. On the single fiber surface forming the fiber bundle, the fiber bundle has a substantially continuous height of 0.5 in the longitudinal direction of the fiber bundle. ~ 1.0 # m of crepe 2 ~ 15 锢. The present invention has observable convex portions in the longitudinal direction of the continuous fiber in the range of 10 ^ ιπχΙΟαβ, which is not specifically selected, and is defined herein with a predetermined "crepe", and counts the number. Because of the existence of this crepe, the acrylonitrile rayon fiber bundle of the present invention has a specific good bundling property, and the fiber with the fiber bundle as a precursor is used for manufacturing static pre-fibrillation printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In order to develop the easy-to-low dimension of the time beam, it is too delicate, and the degree should be increased to increase the texture, and the crepe comes from the surface. The table shows the low physical properties. The fiber bundles made by the soaked fiber-reduced pre-opening fiber bundles are well made, and when collected well, they are good. They show that the high-stranded silk is too dimensional, and when the fiber is attached to the fiber, it is highly effective. Dipping in the sulphur pattern, striatum ... Pre-electric crepe drive This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) 472090 A7 B7 V. Description of the invention (5) Therefore, the height of the crepe M 0.6 to 0.8 wm is good. As for the width of the crepe, it is about 0.5 ~ l.Owm, preferably 0.6 ~ 0.8 / ^ 1 «. (Please read the precautions on the back before filling in this page.) When the number of crepe is too large, the surface area of the fiber bundle will increase, and static electricity will easily occur, which will cause the bunching property of the fiber bundle to decrease. When the number of the crepe is too small, the crepe has a good bundle property, and M and the carbon fiber yarn using the fiber bundle as a precursor can obtain good fiber openness when manufacturing a prepreg. Therefore, on the surface of the single fiber bundle constituting the fiber bundle of the present invention, it is necessary to have 2 to 15 crepe lines, and preferably M 1 to 2 to 15 pieces. In addition, the number of crepe stipulated in the present invention does not necessarily mean that all the single fibers constituting the fiber bundle have a trend of this amount, which is 80% Μ, preferably K 90¾ Μ, and more preferably 95¾ Μ. It is sufficient for a single fiber to have this number of ridges. Furthermore, the fiber bundle of the present invention must have an iodine absorption amount per unit fiber weight of 0.5 to 1.5% by weight, and preferably 0.5 to 1.0% by weight. This amount of iodine absorption is a measure of the density of the acrylonitrile-based fiber bundles, and it is a value measured in accordance with the following iodine absorption method as disclosed in JP-A-Sho 6 3-8 5 168. The method for measuring iodine absorption is printed by a precision scale printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A dry sample with a fiber length of 5 to 7 cm is about 0.5 g. It is placed in a 200 ml conical flask with a common column. 100 ml of iodine solution (weigh 12.5 grams of I, 10 grams of 2,4-dichlorophenol, 90 grams of acetic acid, and 100 grams of potassium iodide, transfer to a 1-liter graduated cylinder, and dissolve with water to make a quantitative 1-liter iodine solution). After shaking at 60 ± 5 ° C for 50 minutes, after absorbing treatment, the iodine-absorbing sample was rinsed in running water for 30 minutes, and then centrifuged (2 000 rpm X 1 minute). Air-dried, accurately weighed to find the weight increase. -7- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 472090 A7 _B7_ V. Description of the invention () < Please read the note on the back first? Please fill in this page again if the value of iodine absorption of the fiber bundle is too small, which means that the fiber bundle is too dense, that is, the surface density of the fiber is high, and the shape of the fiber surface is smooth, which is not suitable. On the other hand, when the iodine absorption value of the fiber bundle is too large, it means that the density of the fiber surface is too low. In this way, the drying load when preparing the acrylonitrile rayon fiber bundle is large, and the problem is that the spinning speed cannot be increased. Moreover, the strength of the calcined sulfonate filaments was too low. The acrylonitrile rayon fiber bundle of the present invention is constituted as described above. Any tow having a total denier of more than 30,000 (total fineness of 33,000 dtex) has a good bundling property, and the fiber density can be calcined by the fiber bundle. Therefore, the effect of the present invention capable of high-density calcination is most effective with fiber bundles having a total fineness of 55,000 dtex or more. In addition, when the electrostatic charge of the fiber bundle according to the present invention is measured in the range of -lkV ~ + lkV according to the following measurement method, it is beneficial to improve the bundle property of the fiber bundle. Especially when the electrostatic charge is in the range of -5 kV to +0.5 kV, the fiber bundles are extended, so that the single fiber is less damaged, and there is no degradation in performance, and stable high quality can be maintained. Measurement method of static lightning and thunderstorm. Two iron two clamps with hard chrome plating on the surface are set 60 meters apart from each other. The acrylonitrile fiber bundle of the measurement object passes between the clamps and is taken up by the Ministry of Economic Affairs ’intellectual property. Printed by the Bureau ’s Consumer Cooperatives, ir will not change when measured. S. On the basis of piezo-electricity, there are 5 rows of electric tapes for the electric system, and the electric wire = 5 Π fixed static beam ni stable static dimension B / beam ldo fiber 50 rows dimension hi 糸 to bundle fiber is nitrile beam dimension 糸 sh Acrylic fiber, acrylic fiber, acrylic fiber, styrene, acrylic acid, nitrile is allyl allyl, which should be divided into one, the public order let the value of 10 test, before pressing the piezoelectric rod of its electric band clamp III The paper size of this paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 472090 A7 B7 V. Description of the invention (Printing of U.S. oil, etc. by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, etc.) Once the solution is agglomerated, the strength of liquid 8 fiber is strong. The amount of retinal nitrile has a high coagulation rate to make the solvent dissolve and the other %% solids. This succinctide is an agent at the 70th level. The vinylene contains a heavy weight. The ester has the pressure of cellulose nitrile, and the three-solvent fiber is at the 70th degree of the family. The pressure is 50%, the pressure of the liquid puller is extended. The pressure is 50% of the original nitrile pressure, and the concentration of nitrile is 50%. The sesquiterene and degree group crude oils contain high-fibrillated fiber propene propene agent liquid spinning product ρϋ propionitrile liquid concentrate, and the nitrile carbon is dissolved with propene fiber to condense the 50-3 propene agent liquid. Spinning agent is obtained by spinning on the spinning machine before spinning. The spinning yarn is melted and dissolved in the fiber, which can be driven by oil and acrylic to obtain a solid solution. 301. The spinning yarn on the spinning machine is also fed into the high-firing precursor fiber. % The second nitrile coagulated before the application of M to obtain a solid solution, the ester extraction of carbon content of the second dose of the machine from the solid degree of the second solution of the coagulation of the vitamin family, but the beam fibrous redissolve orderly C, temperature, fiber amount of the first machine, this fiber Waifangfangwei carbon hair 95 Institute, rapid dissolution, medium carbon re-dissolved to make the system, the agent fiber has a substance ° 0 silk dissolve%. Liquid Ming Nitrogen is used as the oil of 95. It is made with 50% solids and a certain amount of solid hair. There is a substance called p. 50 solid propylene fluorene ketones are described as follows, at 糸 30 for 70 nd in the order of the two ~ ~ Ming Ming ketone silicone propyl, said that the dissolved nitrile in the M, ~ ~ ', at 糸 30 for Power generation silicon, the rate of M before the material of the former method, Bess 50 outside the soluble nitrile The cost comes with the opposite. Its solidity is 8 ° C, which is the solidity of this method, and it has a solidity of this method. -------- > Clothes · .------- Order · ------- I (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 472090 A7 _B7_ V. Description of the invention () (Please read the precautions on the back before filling in this page) Pull from the first coagulation liquid at the speed less than twice, and then The coagulated silk was subjected to 1.1 to 3.0 times of a second coagulation solution composed of an organic solvent aqueous solution containing a third organic solvent having a concentration of 50 to 7% by weight and a temperature of 30 to 50 ° C, obtained by dissolving the acrylonitrile polymer. Stretch, and then perform moist heat stretching more than 4 times. The first to third organic solvents used in the present invention are all organic solvents that can dissolve acrylonitrile polymers, such as dimethylacetamide, dimethylformamide, dimethylformamide, and the like. The spinning dope may be an organic solvent solution obtained by dissolving an acrylonitrile strip polymer in a first organic solvent. The first organic solvent is particularly dimethylacetamide. "Not only does the spinning dope have good spinnability without deteriorating the spinning dope performance due to the hydrolysis of the solvent, and it can be obtained after the acrylonitrile hafnium fiber bundle is calcined. Stable fiber. The spinning nozzle used to squeeze out the spinning dope can use acrylonitrile strip fiber bundles. When spinning, it has the pore diameter for the production of propylene single fibers with a general thickness of about 1.Qdtex, that is, the spinning of 15 ~ 100 # m orifices. mouth. In particular, since the "drawing speed of the coagulated yarn / the linear speed of the spinning dope extruded from the nozzle" is 0.8 or less, the relationship of good spinnability can be maintained, so that the use of a nozzle with a hole diameter of 15 to 50 ab Spinning mouth is particularly good. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the conditions of the first coagulation liquid and the second coagulation liquid and the extension conditions in the second coagulation liquid specified in the present invention have the effect of improving the orientation of the obtained acrylonitrile strip fiber bundles. importance. The concentration of the second organic solvent in the first coagulation liquid and the concentration of the third organic solvent in the second coagulation liquid are both 50 to 70 weight χ, in order to make -1 0-This paper size applies the Chinese National Standard (CNS ) A4 specification (210 X 297 mm) 472090 A7 B7 V. Description of the invention (Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has a thermostat. There are external and medium, the dissolving from the first is the empty-hand warm concentration agent, the liquid three solid-liquid agent silk machine. The small, elongating preparation dissolves in the solid state with the solid state of the solid solution. The solution can be extended to control the dissolving machine. Phase Congeal to homogeneity. The condensing machine coagulates in the middle state to make the original, and also the easy machine has a good about two one uniformly with the liquid solid, such as silk good, medium capacity W large first silk third and solid silk, spinning as The intermediate and internal solids in the silk liquid are solid, and the solidity is reduced by the solidity. The intermediate liquid is solidified and warmed. The coagulation rate is 10% of the solidification rate. In particular, in addition to dissolving the first solid point of the wire, the second solidification amount of the solidified solid is: The state of coagulation, double coagulation, and solidification in the surface also have its 03 shape in the second, third, and second coagulation in the phase of the super surface liquid coagulation. It should be this second. Out of the solid. Ragu is especially on the bulging, and the solid i3 type, such as the use of diamine extraction silk coagulation for good coagulation. General solid coagulation of liquid D species. The liquid concentration is solid and the medium is uniform, and the original coagulation is solidified, and the agent is good. The liquid M is the solidity of the solid liquid, and the silk is the same. In the solidification of the solid-liquid and solid-solid filaments from the elongation, the i-machine is the same as the silk-solvent and the first, and the coagulant coagulation coagulation and solidification behavior is heavy. The silk ci > Solid ο evenly condensate this condensate into the same 5, solid 5T, similar back, mechanical use, the state of the condensate is present, the person who enters the silk phase is condensed to the outside seed, this is easy to do, the medium and other liquids should be once contained Stretching and solidifying, the difference is worse than the content of this agent, the content of the two capitals is thick, and the solid is solidified from the first shape, and the solid phase is solidified. Note on the back? Please fill in this matter I) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 472090 A7 B7 V. Description of the invention (10 Wi-Fi fiber when printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The second extension of the fiber in the olefin is connected to the sensible heat and the fiber will be 1 糸. Because of the bundle dimension, the first extension may meet the C, and when the extension is wet into the single 1 nitrile, the fiber is dry and the extension will occur. The liquid is dried in olefinic fibers: the total length of the hair washing step is 3. The hair solidity rate is C. The state is the elongation of the liquid with water. The number is easily condensed to the extended state. Additions like this. After the fiber system is made, the fixed beam double volume is extended into a bundle-like expansion. 'Fang, the sexual extension is like a sudden condensation and extension. The extension and expansion of the bundle after expansion and expansion are delayed. In the course of stretching, the stretched and stretched shape of the swelled and expanded M fiber is considered to be a stretch. Deferred times. The high-moisture and low-strand extension of the final fixed fiber is collected in the silk during the non-nitrile super-step. After the nitrile is formed, the thermal expansion of the dimensional heat is reduced and the dimension is reduced. That is, the dope is stretched and the dope is stretched. At the same time, the state 圼 圼 drying fiber solution was also extended and solidified by Cyanyan, and Cyanyan was extended. Shaped and dry. The extension of the green heat times without condensation after the expansion of the number of bundles to expand into a solid eye, good extension of solidification and humidity4, the two-step expansion solution in the middle step of the expansion of the complete recovery of the two, the heat-coagulation, etc. In the first step of the hair extension step, the solid standard solution is a fibrous water stretch, but the wet stretch of the third method is raised. The middle extension is solidified into the system and is boiled, resulting in the side extension of the middle extension or the causal solution extension of the two, the coagulation of the nitrile junction or the middle extension of the K, above the liquid water. Difficult to crack solid-liquid thermal di-dry diene stretched in the middle of elongation, elongation M, solid boiling hair breaks to the direction of solidification wet in the dry di-propylene extension water solid M electric ex-beam ductile coagulation in the dimension, fixed The second condensation is, after the heat is condensed and the static dt dimensional heat is 4 bundles. The second highest order of the wet time is the wettable liquid in the second after the 00 fiber wet set. For example, split the single bundle in the first mention of its washing, also in the standard solid or dry hair, 0 进 into the low _, the broken M dimensional is in the water, the condensation, dry easy 33 nitrile picking down (please read the back of the first Note: Please fill in this page again.) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 472090 A7 B7 11 V. Description of the invention () The extension of the extension can be determined appropriately, such as 8 times or less. (Please read the precautions on the back before filling in this page.) Furthermore, in the production method of the present invention, the swelling degree of the expanded fiber bundles before drying after stretching is 70 weights: or less, and the fiber bundles are used as precursors. It is better that sulfonate yarn becomes a high-performance fiber yarn. Since the coagulation yarn is produced in the first coagulation liquid, the "drawing speed of the coagulation yarn / the linear velocity of the spinning dope from the nozzle" is reduced, making the first The coagulated filaments in the coagulation liquid can be uniformly coagulated, and when stretched in the second coagulation liquid, the filaments are uniformly oriented to the inside, so that the swelling degree of the expanded fiber bundles before drying after the stretching is 70% by weight or less . That is, when the coagulated yarn is produced in the first coagulation liquid, if "the coagulation yarn drawing speed / the linear velocity of the spinning dope extruded from the nozzle" is increased, the coagulated yarn in the first coagulation liquid is simultaneously coagulated and stretched. , Will make the coagulation of the coagulation filaments in the first coagulation liquid uneven. Therefore, even if it is drawn in the second coagulation liquid, the swelling degree of the swelling fiber bundle before the drying after the drawing is low, that is, the yarn cannot be formed uniformly to the inside. However, the swelling degree of the fiber bundles in the swollen state before drying was set to a centrifugal separator (30GGrpm, 15 minutes) after removing the fiber bundles in the swelled state, and the weight was W, and dried in a 1 1 ° C hot air dryer The weight after 2 hours is W 0, then the value obtained by the following formula is: The swelling degree printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, U) = (W-W0) X / W0 In the manufacturing method of the present invention, After the fiber bundle is stretched in the second coagulation liquid, or after being stretched in the second coagulation liquid, the fiber bundle after the wet heat stretching is dried by a known drying method to obtain the target acrylonitrile fiber bundle. And because the acrylonitrile fiber bundle of the present invention is dense, high productivity can be obtained. -13- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 472090 A7 _B7_ V. Description of the invention () (please First read the note on the back? Matters and then fill out this page) Therefore, not only can the above high-performance sulfonate precursor be used to obtain high strength, produce chemical resistance of acrylonitrile, and also be used as short-cut fibers. Used as a reinforcing fiber in industrial materials. The invention of the Mu-Jia shape energy will be described with reference to the following examples. In the embodiment, the observation of the crepe is to use a surface scanning electronic display microscope to observe the fiber surface morphology at a high magnification. On a fiber surface that is not specifically selected, 1G 乂 mxi0; in the range of um, count the continuous observation of the crease in the longitudinal direction. . Example 1 Take acrylonitrile, methyl acrylate, methacrylic acid, ammonium persulfate-ammonium bisulfite, and ferric sulfate, and copolymerize by hydroponic suspension polymerization to obtain acrylonitrile units / methyl acrylate units / methacrylic acid units = 9 5 / 4/1 (weight) acrylic copolymer. This copolymer was dissolved in dimethylacetamide to prepare a spinning dope having a concentration of 21% by weight. This spinning dope passed through a spinning nozzle with a hole number of 50, 0 0 0 and a hole diameter of 6 0 # m. It was pressed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to print the structured liquid. · Yanshui dope% Yannamine is a solid amount of Yanshui reel. It is boiled and solidified in a solution of 65. It is condensed at the base. It should be concentrated. Solid speed 3 coagulation 2 coagulation pull degree 2 extension weight is 65 times as long as the temperature extension of the pumping temperature, 4 lead to the same concentration in the 0. guide group, ， the solution of the liquid washing P solidity contact with water 35 coagulation The speed of silk silk line of steroids. Wendi's condensate is twice as high as this, and its 5 output is C-based C2. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 472090 A7 B7 V. Description of the invention (after 13 1C Treatment 1 strong oil-vitamin-fiber
此 束 , 隹 燥維 2纖 I ftΜ/ / 卩腈 力烯 棍 Λ、丙 ^的 X 捲 機 取 捲 經 單 得 速 絲 纺 终 最 糸 腈 烯 丙 該 在 好 良 態 狀 燥 乾 的 束 、U44 維 纖 系 0 η 腈 mi烯 m/丙 80得 為所 度 高 而 續 連 上 質 實 有 向 縱 束 維· 纖。 於在 ，存 面個 表 5 維紋 纖縐 單的 之η 東 維1 纖度In this bundle, the two-fiber I fiber ft // 卩 Nitrile allyl Λ, propyl ^ X winder take-up and wind through the single-speed silk spinning, the final cyanonitrile ally should be dried in a good state, U44-dimensional fiber system 0 η nitrile miene m / propane 80 can be connected to a high-quality directional longitudinal fiber. In the table, there is a table of 5-dimensional texture, fiber crepe, single η, and 1-dimensional fineness.
W 維束 纖維 位纖 單糸 每腈 ，烯 量丙 碘的 吸後 之伸 束延 維熱 纖濕 系而 睛 烯 ％ 丙量 此重 量 ο 測 1 ，為 外 ％ 另 量 重 得 所 燒 煆 束 維 纖 系 腈。 烯 2 丙mm b / ¢ ε f)k un o 再40 , 為 % 度 量強 重條 5 fch 6 絲 為的 度絲 潤維 膨纖 之碳 數 孔 過 通 液 原 絲 纺 之 製 raM- 1X 例 胞 實 令 徑 孔W-dimensional bundle fiber single fiber per unit of nitrile, propene iodide after the extension of the fiber extension of the thermal fiber wet system and the percentage of propylene content of this weight ο measure 1, as the outside weight and the weight of the burned bundle Vinyl cellulose nitrile. Ene 2 propylene mm b / ¢ ε f) k un o then 40, is a% measurement of heavy weight 5 fch 6 silk is the degree of silk moisturizing and expanding fiber carbon number holes through liquid-through raw silk spinning raM-1X Example Cell hole
基. 甲二 的 % 量 重 ο 6 度 濃 P 5 3 度 溫 於 出 壓 嘴 纺 的 m JU 凝第度 此該濃 ，從 ， 絲度 P 固速40 凝拉度 為抽溫 成倍至 ， 3 弓 中ο 導 液之著 固度接 凝速絲 一 線固 第的凝 之出此 成壓。 構液拉 液原抽 溶絲中 水纺.液 胺M固 醯絲凝 乙固一 在 液 固 凝二 第 之 成 組 液 溶 水 胺 醯 乙 基 甲二 的 量 重 伸 延 時 同 洗 水 行 進 次。 其倍 0 5 倍2 2 伸 1.延 伸中 延水 中沸 液於 再 倍 (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 後ld rrn*—♦ 理 1 處度 劑強 油維 纖Basic. The weight of the second% ο 6 degrees thick P 5 3 degrees warmer than the m JU solidification of the spinning nozzle. This should be thick, from the silk degree P solid speed of 40, the degree of condensation is doubled to the temperature, 3 In the bow, the solidity of the guide fluid is connected with the solidified solid wire, and the solidified solid is formed. The structure of the liquid-drawing liquid draws the silk in the spinning. The liquid amine M is fixed and the silk is condensed and the solid is solidified. . Doubled 0 5 times 2 2 Stretched 1. Extend the boiling water in the medium-long extension water again (please read the note on the back? Matters before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs ld rrn * — ♦ Management 1 agent strong oil fiber
捲 經束， 隹 燥雒 汔纖 rft Μ 青 Π I 力烯 輥 ί Λ,丙 熱 W X 取 捲 機 單 得 速 絲 纺 终 最 糸高 腈而 烯續 丙連 該上 在質 ，實 好有 良 向 態縱 狀束 煉維 乾纖 的於 束 ， 維面 纖表 。 糸維 n°睛纖 E 稀單 m/丙之 80得束 為所維 度 纖 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7 五、發明說明（ 14 維束 纖維 位纖 單糸 .每腈 ，烯 量丙 碘的 吸後 之伸 束延 維熱 。 纖濕 在糸而 存腈 ， 個烯.％ 3 丙量 紋此重 總量 8 的消 ο η ，為 外纟 ο 另量 度· 重 得 所 燒 烺 束 維 纖 糸 睛 〇 烯 2 丙mm 此g/ 將ok 再41 , 為 度 量強 重條 65絲 為的 度絲 潤維 膨纖 之碳 - 得 銨 ， 酸合 硫聚 過共 用法 使 合 、 聚 酸浮 烯懸 丁 \糸 里(水 、 用 酯利 甲 ， 酸鐵 烯酸 丙硫 Λ' 腈銨 3稀氫 例丙酸 施取硫 實 亞 \ 基 2 Ϊ \ 6 二 =9於 位溶 單物。 酸聚液 烯共原 丁該絲 異將纺 \ 。 之 位物 ％ 單聚量 酯共重 甲 糸 2 酸腈度 烯烯濃 丙丙成 \ 之製 位成調 單構 ， e:)胺 量 ®_ _ 丙(S乙 2 (請先閱讀背面之注咅？事項再填寫本頁) 嘴 纺 的 液原 溶絲 水纺 胺 Μ 醯絲 3 乙固 LO 基凝 徑甲此 孔二 ， 、 的絲 ο % 固 ,0量凝 LO 重為 數65成 孔度 ， 過濃中 通，液 液 V 固 原30凝 絲度一 纺溫第 此於之 出成 壓 構液 拉甲 油二 中的 液 ％ 固量 凝重 一 5 i 6 第度 該濃 從 ， 度 V 速35 拉度 抽溫 倍至 3 引 ο導 之著 度接 速絲 線固 的凝 出此 壓 〇 倍 2 伸 1.延 伸中 延水 中沸 液於 在再 液倍 固 ο 12 二伸 第延 之時 成同 組 ， 液洗 溶水 水行 胺進。 釀次倍 乙其 ΙΛ 基。2 經濟部智慧財產局員工消費合作社印製 後1C 理 1 處度 劑強 油維 纖 單 得 速 絲 取坊 捲终 最 機 $ 時 取t 捲 經束 , 隹 燥雒 訖纖 K斧 卩腈 力晞 輥 _ ^丙 ΜΧΘ e 為 度 糸高 腈而 烯續 丙連 該上 在質 ，實 好有 良 向 態縱 狀束 燥維 乾纖 的於 束 ， 維面 纖表 糸維 腈纖 烯單 丙之 得束 所維 纖 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7__ 五、發明說明（） 度0.7wm的縐紋4個存在。 (請先閱讀背面之注意事項再填寫本頁) 另外，測量此丙烯腈糸纖維束之吸碘量，每單位纖維 重量％為0 . 8重量％ ，而濕熱延伸後的丙烯腈糸纖維束 之膨潤度為6 1重量％ ，再將此丙烯腈系纖維束煅燒所得 碳纖維絲的絲條強度為4 2 0 k g / m m 2 。 窖朐例4 取丙烯腈、丙烯酸甲酯、異丁烯酸、使用過硫酸銨-亞硫酸氫鏡、硫酸鐵，利用水糸懸浮聚合法共聚合，得 丙烯睛單位/丙烯酸甲酷單位/異丁烯酸單位=9 6 / 3 / 1 (重量）構成之丙唏腈糸共聚物。將該共聚物溶於二甲基 乙醯胺，調製成濃度2 1重量％之纺絲原液。 此纺絲原液通過孔數5 0 , 0 0 0、孔徑4 5 w m的纺嘴，壓 出於溫度3 5 υ ,濃度6 0重量％的二甲基乙醯胺水溶液構 成之第一凝固液中，成為凝固絲，此凝固絲以纺絲原液 壓出的線速度之0 . 3倍抽拉速度從該第一凝固液中抽拉 。此凝固絲接著導引至溫度3 5 °C ,濃度6 0重量％的二甲 基乙醯胺水溶液組成之第二凝固液，在液中延伸2.0倍 。其次進行水洗，同時延伸2 . 0倍，再於沸水中延伸 2 . 5 倍。 經濟部智慧財產局員工消費合作社印製 油劑處理後，Μ熱輥加Μ乾燥，經捲取機捲取，得單 纖維強度1 . 1 d t e X的丙烯腈系纖維束，此時最終纺絲速 度為 80(n/min。 所得丙烯腈糸纖維束的乾燥狀態良好，在該丙烯腈系 纖維束之單纖維表面，於纖維束縱向有實質上連續而高 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7 五、發明說明（） 度0.7a B的縐紋5個存在。 另外，測量此丙烯腈条纖維束之吸碘量，每單位纖維 重量％為〇.7重量，而濕熱延伸後的丙烯腈糸纖維束 之膨潤度為61重量：ϋ ,再將此丙烯腈条纖維束煅燒所得 磺纖維絲的絲條強度為4 2 0 kg/mni 2 ^ fch較例1 按實施例1同樣方法從第一凝固液抽拉凝固絲後，不 用第二凝固液，就在大氣中延伸1.2倍，再水洗，同時 延伸2·0倍，又在沸水中延伸2.5倍。繼而與實施例1 同樣，經油劑處理後，以熱棍進行乾燥，以捲取機捲取 ,得單纖維纖度l.ldtex的丙烯腈糸纖維束。此時最終 紡絲速度為60m/min。 所得丙烯腈条纖維束的乾燥不充分，於該丙烯腈条纖 維束的單纖維表面，於纖維束縱向有不連續而高度0.4 A m的縐紋18個存在。且此丙烯腈条纖維束充分乾燥後 煅燒所得磺纖維絲的絲條強度為380 kg/mm 2。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 不時 1 , 同例 後，施 絲洗實 固水與 凝再又 拉 〇 〇 抽倍倍 液 C- 5 固 1 2 凝伸伸 一 延延 第中中 從氣水 法大沸 方在在 樣就著 同，接 1 液 ， 例固倍 施凝 4 實二1. 按第伸 用延 後ldn 理1.mi 處度m/ 劑纖60 油維為 經纖度 , 單速 樣得絲 同，紡 取 捲 機 取 捲 以 燥 乾 行 進 棍 熱 以 終 最 時 此 ο 束 維 纖 糸 腈 烯 丙 的 有量 向测 縱 ， 束外 維另 线 錄 ο 在在 ，存 面個 表 6 維紋 纖绡 眞 θ Ma 的 束 '一工一 舖 ο 纖度 糸高 腈而 烯績 丙連 得上 所質 實 /ω 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 B7_ 17 五、發明說明（） 此丙烯腈糸纖維束的吸碘量，每單位纖維重量為2.0重 量％ 〇 (請先閱讀背面之注意事項再填寫本頁) 又，濕熱延伸後的丙烯腈条纖維束之膨潤度為8 5重量％ ，而且此丙烯腈条纖維束煆燒所得碳纖維絲之紡絲強度 為 390kg/mm2 〇 hh較例3 按實施例1同樣方法從第一凝固液抽拉凝固絲後，接 著在溫度3 5 °C ,濃度6 0重量％二甲基乙醛胺水溶液組成 的第二凝固液中延伸4 . 0倍。再水洗，同時延伸.2 . 0倍 。又在沸水中延伸2. 5倍之際，於沸水延伸步驟中，發 生丙烯腈糸纖維束之單纖維斷掉和起毛，致紡絲中斷。 I:卜，齩例4 按實施例1同樣方法從第一凝固液抽拉凝固絲後，接 著引導至溫度35°C ,濃度60重量S；二甲基乙醯胺水溶液組成 的第二凝固液中。在液中霄試延伸5.0倍，但在第二凝 固液中發生單纖維斷掉和起毛，致紡絲中斷。 實施例1和比較例1之S E Μ (表面掃描型電子顯微鏡） 照Η，分別如第1和2圖所示。 產業h刺用僧倌 經濟部智慧財產局員工消費合作社印製 本發明碳纖維前驅體用丙烯腈条纖維束，其集束性優 良，且緻密性優異，乾燥負荷小。 因此，即使總纖度3 3，0 0 0 d t e X以上的纖維束，紡絲速 度不會下降，製造效率良好。 另，按照本發明傜總纖度33,000dtex以上之纖維束， -1 9 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 A7 _B7_ 五、發明說明（） (請先閱讀背面之注意事項再填寫本頁) 以此為前驅體之磺纖維絲於成型之際，不必採取將磺纖 維絲數支拉齊之步驟，可以避免成型品製造手續複雜和 成本高昂。 .再者，本發明磺纖維前驅體用丙烯腈条纖雒束，由於 每單位纖維重量的吸碘量為0.5〜1.5重童S：範圍，加以 煆燒即可得高強度的磺纖維絲，按上逑不但具有優良集 束性，且使用以此為前驅體的磺纖維絲製造預浸物時， 開纖性良好。 再者，按照本發明磺纖維前驅體用丙烯腈糸纖維束之 製法，可容易且安定製造上述緻密性優良，乾燥負荷性 小，而且集束性優，適用做磺纖維絲前驅體之丙烯腈条 纖維束。 圖忒簡Μ說明 第1圖為實施例1的碳纖維前驅體用丙烯腈糸纖維束 之SEM照片； 第2圖為比較例1的磺纖維前驅體甩丙烯聘糸纖維束 之S Ε Μ照片。 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472090 今 a πThe warp bundle, rft Μ green Π I, ene roller, Λ, acrylic heat WX take-up machine to obtain the highest spinning speed of the final silk nitrile, but the acrylic continuous quality should be good Longitudinal bundles are used to make the bundles of dry fiber, and the surface of the fiber is straight.糸 dimensional n ° eye fiber E dilute single m / c 80 of the bundle is the size of the fiber paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 472090 A7 B7 V. Description of the invention (14-dimensional bundle Fiber position fiber single unit. Per nitrile, propene iodide elongation and extension heat after absorption. The fiber is wet while the nitrile is stored, and the unit is ene.纟 ο Measure and regain the burnt fiber bundles. 2 ene mm 2 g / g This will be ok and 41, which is a measure of the strength of the 65-strength fiber bulk fiber. Acid sulfur sulfide polymerization is used in combination, polyacid succinic acid, butadiene (water, with ester methyl ester, acid ferric acid propylsulfuric acid Λ 'nitrile ammonium 3 dilute hydrogen example propionic acid application thiocitrile radical 2 Ϊ \ 6 == 9 soluble in-situ single substance. Acid polyliquidene co-ordinary butadiene will be spun \. Positions% Monomer esters co-weight formamidine 2 Acrylonitrile alkenyl propylene propylene into The system is adjusted to a monotonic structure, e :) Amine ® ® _ propyl (S B 2 (Please read the note on the back? Matters before filling in this page) Ammonium succinate 3 Ethyl-LO-based coagulant A. This pore is 2% solid, 0% condensed LO weighs 65% of the porosity, is too thick and medium, liquid-liquid V Guyuan 30, and the silk degree is a spinning temperature The result is the liquid% solids in the pressure-contained liquid nail polish II. The solid weight is a weight of 5 i 6. This concentration is from the degree of V. The speed is 35. The temperature is drawn to 3 times. The solidified condensate pressure is 2 times the extension 1. The boiling liquid in the extension medium is re-liquid solidified at the time of the second extension. 12 The second extension is the same group, and the water is washed and dissolved in water to proceed the amine. 2. After printing by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, 1C processing, 1 place, strong oil, fiber, single fiber, single-speed wire, and paper rolls. The last machine is $. Take the warp beam, and dry it. Nitrile strength roller _ propyl MXX θ e is the degree of high nitrile and the propylene is still qualitative, there is a well-oriented longitudinal bundle of dry and dry fiber. The size of the single fiber paper used by Shan Bingzhi is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 4720 90 A7 _B7__ 5. Description of the invention () There are 4 crepe with a degree of 0.7wm. (Please read the precautions on the back before filling this page) In addition, measure the iodine absorption of this acrylonitrile fiber bundle, per unit fiber weight % Is 0.8% by weight, and the swelling degree of the acrylonitrile fiber bundle after moist heat stretching is 61% by weight, and the strand strength of the carbon fiber filament obtained by calcining the acrylonitrile fiber bundle is 4 2 0 kg / mm 2 . Example 4: Acrylonitrile, methyl acrylate, methacrylic acid, ammonium persulfate-bisulfite mirror, and ferric sulfate were used to copolymerize by the hydroponic suspension polymerization method to obtain acrylonitrile units / methacrylic acid units / methacrylic acid units = 9 6/3/1 (weight) of acrylonitrile fluorene copolymer. This copolymer was dissolved in dimethylacetamide to prepare a spinning dope having a concentration of 21% by weight. This spinning dope passed through a spinning nozzle having a hole number of 50, 000, and a hole diameter of 45 wm, and was pressed into a first coagulation solution composed of an aqueous solution of dimethylacetamide at a temperature of 35 υ and a concentration of 60% by weight. , Becomes a coagulated yarn, and the coagulated yarn is drawn from the first coagulation liquid at a drawing speed of 0.3 times the linear speed of the spinning original hydraulic pressure. This coagulated filament was then guided to a second coagulation liquid consisting of an aqueous solution of dimethylacetamide at a temperature of 35 ° C and a concentration of 60% by weight, which stretched 2.0 times in the liquid. It was then washed with water and stretched 2.0 times at the same time, and then stretched 2.5 times in boiling water. After processing the printed oil agent by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the MH hot roll was added with MH and dried by a winder to obtain an acrylonitrile fiber bundle with a single fiber strength of 1.1 dte X. At this time, the final spinning speed It is 80 (n / min.) The obtained acrylonitrile fiber bundle has a good dry state. On the single fiber surface of the acrylonitrile fiber bundle, there is a substantially continuous and high -17 in the longitudinal direction of the fiber bundle. (CNS) A4 specification (210 X 297 mm) 472090 A7 _B7 V. Description of the invention (5) There are 5 crepe with a degree of 0.7a B. In addition, the iodine absorption of this acrylonitrile strip fiber bundle is measured, per unit fiber weight % Is 0.7 weight, and the degree of swelling of the acrylonitrile 糸 fiber bundle after moist heat stretching is 61 weight: ϋ, and then the acrylonitrile strand fiber bundle is calcined to obtain a thread strength of 4 2 kg / mni 2 ^ fch Comparative Example 1 After pulling the coagulated silk from the first coagulation liquid in the same manner as in Example 1, the second coagulation liquid was used to extend 1.2 times in the atmosphere without washing with the second coagulation liquid, and then washed with water, while extending 2.0 times, and then in boiling water. Extended 2.5 times. Then, as in Example 1, After the treatment, it was dried with a hot rod and taken up by a winder to obtain a single fiber fineness l.ldtex acrylonitrile 糸 fiber bundle. At this time, the final spinning speed was 60 m / min. The obtained acrylonitrile strip fiber bundle was not dried. Sufficiently, on the single fiber surface of the acrylonitrile strip fiber bundle, there are 18 discontinuous crepe having a height of 0.4 A m in the longitudinal direction of the fiber bundle. And the acrylonitrile strip fiber bundle is sufficiently dried, and the silk of the obtained sulfonate filaments is calcined. The strength of the strip is 380 kg / mm 2. (Please read the precautions on the back before filling in this page.) Printed from time to time by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Pull 〇〇 draw the double liquid C- 5 solid 1 2 condensate and stretch a stretch of the middle from the gas-water method of the large boiling point in the same as in the sample, then 1 liquid, for example, solid condensate 4 solid second 1. Press The extension stretch is used for ldn treatment 1.mi degree m / dose fiber 60 The oil dimension is the warp and fineness, the same speed is obtained at the same speed, and the reel is taken up by a spinning reel to dry the stick and heat it to the end. Longitudinal measurement of cellulosic nitrile allyl, the outer dimension of the beam is recorded separately. Table 6 Bundles of dimensional fiber 绡 眞 θ Ma 'One job and one shop ο Fineness 糸 High Nitrile and Acrylic Acrylic Reliable / ω This paper size applies Chinese National Standard (CNS) A4 (210 X 297) (Centi) 472090 A7 B7_ 17 V. Description of the invention () The iodine absorption of this acrylonitrile rayon fiber bundle is 2.0% by weight per unit fiber 〇 (Please read the precautions on the back before filling this page). The degree of swelling of the acrylonitrile strip fiber bundle was 85% by weight, and the spinning strength of the carbon fiber yarn obtained by calcining the acrylonitrile strip fiber bundle was 390 kg / mm2. 0hh. Comparative Example 3 was coagulated from the first method in the same manner as in Example 1. After the coagulated silk was drawn by the liquid, it was stretched 4.0 times in a second coagulation liquid composed of a temperature of 35 ° C and a concentration of 60% by weight of dimethylglydiamide aqueous solution. Rinse again while extending .2.0 times. On the occasion of 2.5 times stretching in boiling water, in the boiling water stretching step, the single fibers of the acrylonitrile 糸 fiber bundle were broken and fluffed, causing spinning to be interrupted. I: Bu, Example 4 After drawing the coagulated silk from the first coagulation solution in the same manner as in Example 1, it was then guided to a temperature of 35 ° C and a concentration of 60 weight S; a second coagulation solution composed of an aqueous dimethylacetamide solution. in. The test was extended 5.0 times in liquid, but single fiber breakage and fluff occurred in the second solid solution, resulting in interrupted spinning. S EM (surface scanning electron microscope) photographs of Example 1 and Comparative Example 1 are shown in Figs. 1 and 2, respectively. Printed for industrial h thorns by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The acrylonitrile strip fiber bundle for the carbon fiber precursor of the present invention has excellent bundling properties, excellent compactness, and low drying load. Therefore, even with fiber bundles having a total fineness of 3,0 0 0 d t e X or more, the spinning speed does not decrease, and the manufacturing efficiency is good. In addition, according to the present invention, a fiber bundle with a total fineness of 33,000 dtex or more, -1 9-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 472090 A7 _B7_ V. Description of the invention () (please first Read the notes on the reverse side and fill in this page.) When using this precursor as a precursor for sulfonate filaments, you do not need to take the steps of pulling the sulfonate filaments together to avoid the complicated and expensive manufacturing process of the molded product. In addition, the sulfon fiber precursor of the present invention is bundled with acrylonitrile strips. Since the iodine absorption per unit weight of the fiber is 0.5 to 1.5 weight S: range, high-intensity sulfon fiber filaments can be obtained by calcination. Pressing on the top not only has excellent bundling properties, but also has good fiber opening properties when using sulfonate filaments made from this precursor to make prepregs. In addition, according to the method for preparing acrylonitrile / yarn fiber bundles for sulfo fiber precursors according to the present invention, the above-mentioned excellent compactness, small drying load, and excellent bundling properties can be easily and stably produced, and the acrylonitrile strips suitable for use as sulfo fiber precursors are applicable. Fiber bundle. Brief Description of the Drawings Figure 1 is a SEM photograph of an acrylonitrile 糸 fiber bundle for a carbon fiber precursor of Example 1; and Figure 2 is an S EM picture of a propylene fiber bundle from a sulfon fiber precursor of Comparative Example 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 472090 today a π
五、發明說明（19) 補充的實施例 實施例1 •使用過硫酸銨-亞硫酸氫銨、硫酸鐵，將丙烯腈、丙烯 醯胺 '甲基丙烯酸進行水系懸浮聚合法，得到丙烯腈單 位/丙烯醢胺單位/甲基丙烯酸單位=96/3/1(重量）構成之 丙烯腈系共聚物。將該共聚物溶解於二甲基乙醯胺中， 調製成濃度21重量％之紡絲原液。此紡絲原液通過孔數 50,000、孔徑45μπι的噴絲板，壓出至一由溫度爲35 °C、濃度爲60重量％的二甲基乙醯胺水溶液所組成之第 一凝固液中，而成爲凝固絲，此凝固絲以紡絲原液壓出 的線速度之0.3倍抽拉速度從該第一凝固液中抽拉。此 凝固絲接著導引至溫度爲35°C、濃度爲60重量％的二甲 基乙醯胺水溶液組成之第二凝固液中，在液中拉伸2 . 0 倍。其次進行水洗，同時拉伸2.0倍，再於沸水中拉伸 2 · 5 倍。 油劑處理後，以熱輥加以乾燥，經捲取機捲取，得單 纖維纖度l.ldtex的丙烯膪系纖維束，此時最終紡絲速 度爲80ro/rain。所得到的丙烯腈系纖維束的乾燥狀態良 好’在該丙烯腈系纖維束之單纖維表面，於纖維束縱向 有實質上連續而高度0.8μ m的縐紋8個存在。 測量此丙烯腈系纖維束之吸碘量，每單位纖維重量％ 有0.8重量％。再者，濕熱拉伸後的丙烯膪系纖維束之 膨潤度爲55重量％，再將此丙烯腈系纖維束煆燒所得碳 472090 五、發明說明(20) 實施例6 使用過硫酸銨-亞硫酸氫銨、硫酸鐵，將丙烯腈、丙 烯醯胺、甲基丙烯酸進行水系懸浮聚合法，得到丙烯腈 單位/丙烯醯胺單位/甲基丙烯酸單位=96/3/1(重量）構 成之丙烯腈系共聚物。將該共聚物溶解於二甲基甲醯胺 中’調製成濃度23重量％之紡絲原液。此紡絲原液通過 孔數50,000、孔徑45μιη的噴絲板，壓出至一由溫度爲 4〇°C、濃度爲65重量％的二甲基甲醯胺水溶液所組成之 第一凝固液中，而成爲凝固絲，此凝固絲以紡絲原液壓 出的線速度之0.5倍抽拉速度從該第一凝固液中抽拉。 此凝固絲接著導引至溫度爲401、濃度爲65重量％的 二甲基甲醯胺水溶液組成之第二凝固液中，在液中拉伸 2 · 〇倍。其次進行水洗，同.時拉伸2 . 0倍，再於沸水中 拉伸2 · 5倍。 油劑處理後，以熱輥加以乾燥，經捲取機捲取，得 單纖維纖度l.ldt ex的丙烯腈系纖維束，此時最終紡 絲速度爲80m/min。所得到的丙烯腈系纖維束的乾燥狀 態良好，在該丙烯腈系纖維束之單纖維表面，於纖維 束縱向有實質上連續而高度0.9μπι的縐紋10個存在。 測量此丙烯膪系纖維束之吸碘量，每單位纖維重量％ 有0.6重量％。再者，濕熱拉伸後的丙烯腈系纖維束之 膨潤度爲52重量％，再將此丙烯膪系纖維束煆燒所得 碳纖維絲的絲條強度爲460kg /mm2。 -22-V. Description of the invention (19) Supplementary examples Example 1 • Aqueous suspension polymerization of acrylonitrile and acrylamide 'methacrylic acid using ammonium persulfate-ammonium bisulfite and iron sulfate to obtain acrylonitrile units / Acrylonitrile copolymer composed of acrylamide unit / methacrylic acid unit = 96/3/1 (weight). This copolymer was dissolved in dimethylacetamide to prepare a spinning dope having a concentration of 21% by weight. This spinning dope was passed through a spinneret having a number of holes of 50,000 and a diameter of 45 μm, and extruded into a first coagulation solution composed of an aqueous solution of dimethylacetamide at a temperature of 35 ° C and a concentration of 60% by weight. It becomes a coagulated yarn, and this coagulated yarn is drawn from the first coagulation liquid at a drawing speed which is 0.3 times the linear speed of the spinning original hydraulic pressure. This coagulated yarn was then guided to a second coagulation liquid composed of an aqueous solution of dimethylacetamide at a temperature of 35 ° C and a concentration of 60% by weight, and stretched 2.0 times in the liquid. It was then washed with water, stretched 2.0 times at the same time, and then stretched 2 · 5 times in boiling water. After the oil treatment, it was dried by a hot roll and taken up by a winder to obtain a polypropylene fiber series having a single fiber fineness of l.ldtex. At this time, the final spinning speed was 80 ro / rain. The dry state of the obtained acrylonitrile-based fiber bundle was good. On the surface of the single fiber of the acrylonitrile-based fiber bundle, eight creases with a height of 0.8 m were substantially continuous in the longitudinal direction of the fiber bundle. When the amount of iodine absorption of the acrylonitrile-based fiber bundle was measured, it was 0.8% by weight per unit weight of the fiber. In addition, the swelling degree of the acrylonitrile-based fiber bundle after moist heat stretching was 55% by weight, and carbon obtained by calcining the acrylonitrile-based fiber bundle was 472090. 5. Description of the invention (20) Example 6 Use of ammonium persulfate- Aqueous suspension polymerization of acrylonitrile, acrylamide, and methacrylic acid using ammonium hydrogen sulfate and iron sulfate to obtain acrylonitrile composed of acrylonitrile unit / acrylamide unit / methacrylic acid unit = 96/3/1 (weight) Nitrile copolymer. This copolymer was dissolved in dimethylformamide to prepare a spinning dope having a concentration of 23% by weight. The spinning dope was passed through a spinneret having a number of holes of 50,000 and a diameter of 45 μm, and extruded into a first coagulation solution composed of a dimethylformamide aqueous solution having a temperature of 40 ° C and a concentration of 65% by weight. It becomes a coagulated yarn, and the coagulated yarn is drawn from the first coagulation liquid at a drawing speed of 0.5 times the linear speed of the spinning original hydraulic pressure. This coagulated yarn was then guided to a second coagulation liquid composed of an aqueous dimethylformamide solution having a temperature of 401 and a concentration of 65% by weight, and stretched in the liquid by 2.0 times. It was then washed with water, stretched 2.0 times at the same time, and then stretched 2.5 times in boiling water. After the oil treatment, it was dried with a hot roller and taken up by a winder to obtain an acrylonitrile fiber bundle having a single fiber fineness of l.ldt ex. At this time, the final spinning speed was 80 m / min. The obtained acrylonitrile-based fiber bundle was in a good dry state. On the single fiber surface of the acrylonitrile-based fiber bundle, ten crepe having a substantially continuous height of 0.9 m were present in the longitudinal direction of the fiber bundle. The amount of iodine absorbed by the acrylic fiber series was measured, and it was 0.6% by weight per unit weight of the fiber. Further, the degree of swelling of the acrylonitrile-based fiber bundle after the wet heat drawing was 52% by weight, and the strand strength of the carbon fiber yarn obtained by calcining the acrylonitrile-based fiber bundle was 460 kg / mm2. -twenty two-