201134993 六、發明說明： 【發明所屬之技術領域】 本發明係關於間位型全芳香族聚醯胺纖維。更詳言之 係關於可獲得不含層狀黏土礦物、力學特性優異、且高品 質之製品的新穎之間位型全芳香族聚醯胺纖維。 【先前技術】 由芳香族二胺與芳香族二羧酸二氯化物所製造之全芳 香族聚醯胺耐熱性優異且難燃性優異廣爲人知。另外，此 等之全芳香族聚醯胺可溶於醯胺系溶劑，由此等之聚合物 溶液經乾式紡絲、濕式紡絲、半乾半濕式紡絲等之方法可 得到纖維亦爲周知的。 該全芳香族聚醯胺中，聚間苯二甲醯間苯二胺（ polymetaphenyl ene-isophthal amide)所代表之間位型全芳 香族聚醯胺（以下簡稱「間位芳香族聚醯胺」）纖維可用 作耐熱•難燃性纖維。如此之間位芳香族聚醯胺纖維之製 法，主要可採用下述（a) 、 （b)之2個方法。進而，此 外之間位芳香族聚醯胺纖維之製造法亦提出有（c)〜（e )般方法。 (a)藉由將間苯二胺與異苯二甲酸氯化物在ν,Ν-二 甲基乙醯胺中進行低溫溶液聚合而調製聚間苯二甲醯間苯 二胺溶液，之後’將在該溶液中副生成的鹽酸以氫氧化鈣 中和後獲得含氯化鈣之聚合物溶液，藉由將得到之聚合物 溶液以乾式紡絲而製造間位芳香族聚醯胺纖維之方法〔專 -5- 201134993 利文獻1:特公昭3 5 — 1 4399號公報〕。 (b) 藉由使含有間苯二胺鹽與異苯二甲酸氯化物的 非生成聚醯胺之良溶劑之有機溶劑系（例如四氫呋喃）與 無機酸受容劑以及含可溶性中性鹽之水溶液系接觸，將聚 間苯二甲醯間苯二胺聚合物之粉末單離（專利文獻2 ··特 公昭4 7 — 1 08 63號公報），使該聚合物粉末再溶於醯胺系 溶劑後，於含無機鹽之水性凝固浴中進行濕式紡絲之方法 (專利文獻3 :特公昭4 8 -- 1 7 5 5 1號公報）。 (c) 從以溶液聚合法合成之間位芳香族聚醯胺（ Meta-aramid )溶於醯胺系溶劑之不含無機鹽或僅含微量 (2〜3 % )之氯化鋰的間位芳香族聚醯胺溶液藉由濕式成 形法製造纖維等之成形物之方法（專利文獻4:特開昭50 —52 1 67號公報）。 (d )將在醯胺系溶劑中進行溶液聚合，以氫氧化鈣 、氧化鈣等中和後生成之含氯化鈣與水的間位芳香族聚醯 胺聚合物溶液從孔洞壓入氣體中，使通過氣體中後，導入 水性凝固浴，接著，使通過氯化鈣等之無機鹽水溶液中後 成形纖維狀物之方法（專利文獻5 :特開昭56 — 3 1 009號公 報）。 (e )將在醯胺系溶劑中進行溶液聚合，並以氫氧化 鈣、氧化鈣等進行中和後生成之含有氯化鈣與水之間位芳 香族聚醯胺聚合物溶液從孔洞紡出於含高濃度氯化鈣之水 性凝固浴中後成形纖維狀物之方法（專利文獻6 :特開平8 -074 1 2 1號公報、專利文獻7 :特開平— 8 842 1號公報等 201134993 然而，因上述（a )之方法爲乾式紡絲，從紡絲抽絲 口紡出的纖維狀之聚合物溶液中，從形成的纖維狀物之表 面附近溶劑揮發•乾燥，於纖維表面生成緻密且強固的鞘 層。因此，即使持續使纖維狀物以水洗等進行洗淨，亦難 以將殘存溶劑充分地除去。此外，經（a )之方法所得纖 維因纖維中殘存之溶劑，在高溫環境下使用時產生黃變。 因此，必須避免高溫下之熱處理，結果，有難以高強度化 之問題。 另一方面，因上述（b )〜（e )之方法爲濕式紡絲， 紡絲階段溶劑不揮發。然而，在將成爲纖維狀的聚合物導 入含有水性凝固浴或高濃度無機鹽之水性凝固浴時，溶劑 從纖維狀聚合物表面附近脫離到水性凝固浴内，同時凝固 浴液所含有之水從凝固的纖維狀物之表面附近浸入纖維狀 物之内部，生成強固鞘層。因此，經乾式紡絲法所得纖維 亦同樣地難以將纖維中殘存之溶劑充分地除去，且無法避 免殘存溶劑造成的高溫環境下之著色或變色（尤其黃變） 。因此，即使爲以（b)〜（e)之方法所得之纖維，亦需 要避免高溫熱處理，尙有難以纖維高強度化之問題。 進而，專利文獻8 (特開200 1 - 348 7M號公報）中， 揭示將間位芳香族聚醯胺溶液凝固爲具多孔之纖維狀物後 ，可於該多孔内含凝固液之狀態，或該多孔内含可塑液， 使該纖維狀物在空氣中進行加熱延伸並接著在該多孔内含 凝固液等之狀態下加熱，接著進行熱處理之方法》 201134993 根據專利文獻8所記載之方法，在間位芳香族聚醯胺 溶液經凝固成爲纖維狀物之階段，實質上於表面成爲無鞘 層的多孔質纖維狀物。然而，將含可塑液的該多孔質纖維 狀物加熱，則之後變得難以將溶劑除去，結果，由該方法 得到之纖維亦無法避免殘存溶劑所造成的高溫環境下之著 色或變色（尤其黃變）。因此，即使以專利文獻8所記載 之方法所得之纖維，需要避免高溫熱處理，且尙有纖維高 強度化困難之問題。 專利文獻9與專利文獻10中，記載含有層狀黏土礦物 之間位型全芳香族聚醯胺纖維。專利文獻9與專利文獻1 0 記載之間位型全芳香族聚醯胺纖維經搭配層狀黏土礦物， 成爲殘留溶劑量低的纖維。然而，含有此等層狀黏土礦物 之間位型全芳香族聚醯胺纖維有間位型芳香族聚醯胺特徵 的絕緣性低、進而在切斷加工或撚絲加工時，層狀黏土礦 物脫落、飛散之情形。因此，由絕緣性提升或防止層狀黏 土礦物脫落、飛散觀點，追求更進一步之改良。— 專利文獻1 1中，記載特徵爲於纖維中殘存溶劑量在 1.0重量％以下，3 00 °C的乾熱收縮率在3%以下，且纖維 之破裂強度在3.0cN/ dtex以上的高溫加工性優之間位型 全芳香族聚醯胺纖維。然而，專利文獻11中，並未記載有 破裂強度在4.5 cN/ dtex以上之纖維，對於高溫薄膜之基 布用途或橡膠補強用途所追求之高破裂強度以及尺寸安定 性，追求更提升。 [先前技術文獻] -8- 201134993 [專利文獻] [專利文獻丨]特公昭3 5 — 1 43 99號公報 [專利文獻2]特公昭47 — 10863號公報 [專利文獻3]特公昭48 - 1 755 1號公報 [專利文獻4]特開昭50 - 5 2 1 67號公報 [專利文獻5]特開昭56一 31〇〇9號公報 [專利文獻6]特開平8 — 074121號公報 [專利文獻7]特開平10_ 8 842 1號公報 [專利文獻8]特開2001- 348726號公報 [專利文獻9]特開2007 - 254915號公報 [專利文獻10]特開2007 - 2625 89號公報 .[專利文獻11]國際公開2007/089008號公報 【發明內容】 [發明所欲解決之課題] 本發明有鑑於上述以往技術所成者，其目的在於供保 留耐熱性、難燃性等之間位型全芳香族聚醯胺纖維原來具 有之性質、破裂強度（breaking strength )高且可抑制高 溫下的著色或變色之新穎之間位型全芳香族聚醯胺纖維。 [解決課題之手段] 本發明者們爲解決上述課題，努力地硏究。結果，發 現藉由適當調整成爲不具鞘蕊的緻密凝固形態之凝固浴之 成分或條件、在特定倍率之範圍内進行可塑延伸，進而， -9 - 201134993 適當調整之後的熱延伸條件，可解決上述課題，而完成本 發明。 亦即，本發明爲實質上不含層狀黏土礦物的間位型全 芳香族聚醯胺纖維，而纖維中殘存之溶劑量相對於纖維全 體而言爲1.0質量％以下，且纖維之破裂強度爲4.5〜6.0cN / dtex的間位型全芳香族聚醯胺纖維。 在此，本發明之間位型全芳香族聚醯胺纖維，3 00 °C 乾熱收縮率較佳爲5.0%以下。 另外，本發明之間位型全芳香族聚醯胺纖維，初期彈 性率較佳爲800〜l，500cN / mm2。 [發明效果] 根據本發明，可提供力學特性、耐熱性等良好且纖維 中殘存之溶劑極微量而實質上不含層狀黏土礦物之間位型 全芳香族聚醯胺纖維（尤其，聚間苯二甲醯間苯二胺系纖 維）。本發明之纖維，除耐熱性或難燃性之間位型全芳香 族聚醯胺纖維原來具有的性質外，尙具有強度，且可抑制 高溫下加工及使用中纖維或纖維製品之著色或變色（尤其 黃變）。因此，本發明之纖維在以往的間位型全芳香族聚 醯胺纖維所無法使用之領域亦可使用，其工業上價値極大 [實施發明之最佳形態] <間位型全芳香族聚醯胺纖維> -10- 201134993 本發明之間位型全芳香族聚醯胺纖維具有以下之特定 物性。關於本發明之間位型全芳香族聚醯胺纖維之物性、 構成、及、製造方法等在以下說明。 〔間位型全芳香族聚醯胺纖維之物性〕 本發明之間位型全芳香族聚醯胺纖維爲破裂強度在一 定之範圍且纖維中殘存溶劑之量非常少者。具體上，爲實 質不含層狀黏土礦物的間位型全芳香族聚醯胺纖維，而纖 維中殘存溶劑量爲1.0質量％以下且纖維之破裂強度爲4.5 〜6.0cN/dtex。因此，本發明之間位型全芳香族聚醯胺 纖維即使在高溫下加工及使用，可抑制纖維或製品之著色 或變色。 〔殘存溶劑量〕 間位型全芳香族聚醯胺纖維因一般係由將聚合物溶解 於醯胺系溶劑之紡絲原液來製造，故當然於該纖維中殘留 有溶劑。然而，本發明之間位型全芳香族聚醯胺纖維，纖 維中殘存溶劑之量相對於纖維質量，爲】..〇質量％以下。必 須在1.〇質量％以下，在0.5質量。/。以下更佳。特別佳爲0.01 〜0 · 1質量％。 相對於纖維質量超過1 .〇質量％溶劑殘留於纖維中時， 在超過20(TC之高溫環境下加工或使用時，易黃變，另外 ，明顯強度降低，故不佳 在本發明中，爲使間位型全芳香族聚醯胺纖維中之殘 -11 - 201134993 存溶劑量在1.〇質量％以下’係在特定倍率之範圍内進行可 塑延伸，進而，調整之後的熱延伸條件。 又，本發明中「纖維中殘存之溶劑量」係指使用以下 之方法所得之値。 (殘存溶劑量之測定方法） 在洗淨步驟出口側採樣纖維，並將該纖維以離心分離 機（轉數5,000rPm)離心1〇分鐘，測定此時的纖維質量（ Ml )。將該纖維於質量M2g的甲醇中煮沸4小時，抽出纖 維中之醯胺系溶劑及水。使抽出後之纖維在1 05 °C環境下 進行2小時乾燥，測定乾燥後之纖維質量（P )。另外，將 抽出液中所含有之醢胺系溶劑的質量濃度（C )以氣體層 析法求出。 纖維中殘存之溶劑量（醯胺系溶劑質量）N ( % )使 用上述Ml、M2、P、及C，由下述式算出。 N = [C/100]x[(Ml+M2-P)/P]xl〇〇 〔破裂強度〕 本發明之間位型全芳香族聚醯胺纖維，破裂強度爲 4.5〜6.0cN/dtex之範園。必須在4.5〜6.0cN/dtex之範 圍’以5.5〜6_0〇>1/{^\之範圍爲佳。又更佳爲5.7〜 6.0cN/dtex之範圍、進而以5.8〜6.0cN/dtex之範圍爲佳 。破裂強度未達4.5 cN/ dtex ’所得之製品的強度低，無 "12- 201134993 法耐用於製品用途之使用，故不佳。另一方面，超過 6.0cN/ dtex，則伸度大幅降低，產生製品操作變困難等 問題。 本發明之間位型全芳香族聚醯胺纖維中，爲使「破裂 強度」在上述範圍内，適當調整凝固浴之成分或條件使成 爲不具鞘蕊的緻密凝固形態之，在特定倍率之範圍内進行 可塑延伸，進而，適當調整之後熱延伸條件合適。 又，本發明中「破裂強度」係指依據JIS L 1015，測 定機器使用Instron公司製、型號5 565，使用以下之條件測 定所得之値。 (測定條件） 抓取間隔 ：20mm 初荷重 ：0.044cN(l/20g) / dtex 拉伸速度 ：20mm/分鐘 〔破斷伸度（elongation at break)〕 本發明之間位型全芳香族聚醯胺纖維，破斷伸度以 15%以上爲佳’ 18%以上更佳，20%以上特佳。破斷伸度 未達1 5%時，在紡織等後加工步驟中步驟通過性降低，故 不佳。 在本發明中’間位型全芳香族聚醯胺纖維之「破斷伸 度」’在後述製造方法之凝固步驟中，藉由爲不具鞘蕊之 緻密凝固形態而可控制。爲使爲1 5%以上，將凝固液作成 -13- 201134993 醯胺系溶劑，例如Ν Μ P ( N —甲基一 2 _吡咯烷酮）之濃度 45〜60質量％之水溶液，浴液溫度成爲10〜5〇°c即可。 又’在此「破斷伸度」係指依據；IIS L 1015，以上述 「破裂強度」之測定條件測定所得之値。 〔300°C乾熱收縮率〕 進而，本發明之間位型全芳香族聚醯胺纖維，3 0(TC 乾熱收縮率以5.0 %以下爲佳，1.0〜4.0 %之範圍更佳。300 °(：乾熱收縮率大時，形成之纖維構造體在高溫曝露會產生 纖維之收縮，纖維構造體之設計變得困難。上述乾熱收縮 率特別佳爲0.1〜3%左右。 本發明之間位型全芳香族聚醯胺纖維中，爲使上述 3 〇〇 °C乾熱收縮率爲5.0%以下，在後述製造方法中，可使 熱延伸步驟之熱處理溫度爲3 1 0〜3 3 5 °C之範圍。未達3 1 0 °C則乾熱收縮率變大，比3 3 5 °C高則因聚合物熱劣化而造 成強度降低及著色。 又，本發明中「3 00 °C乾熱收縮率」係指使用以下之 方法所得之値。 (3 00°C乾熱收縮率之測定方法） 在約3,300dtex之絲束上垂吊98cN ( l〇〇g)之荷重， 相互在距離30cm處做記號。將荷重除去後，將絲束放置 於3 0(TC環境下、1 5分鐘後’測定記號間之長度L。將測定 結果L代入下述式所得之値爲3 00°C乾熱收縮率（％ ) ^ "14- 201134993 300°C 乾熱收縮率（％) = [(30-L)/30]xl00 〔初期彈性率〕 進而’本發明之間位型全芳香族聚醯胺纖維，初期彈 性率以 800 〜l，500cN/mm2 爲佳，900 〜l，5 00cN/mm2 之 範圍更佳。初期彈性率在800〜1，500cN / mm2之範圍，則 形成之纖維構造體不易因外力而變形，用於不織布之基布 等時易於確保尺寸精度。 本發明之間位型全芳香族聚醯胺纖維中，爲使上述初 期彈性率爲8 00〜l,5 00cN/ mm2，可在後述製造方法之可 塑延伸步驟，以3 · 5〜1 0.0倍之範圍施加可塑延伸。延伸 倍率未達3·5倍時，未達初期彈性率，另一方面，比1〇.〇 倍高倍率時，易生斷絲，步驟順暢性惡化。 又’在此「初期彈性率」係指基於JIS L 1015，以上 述「破裂強度」之測定條件測定所得之値。 〔剖面形狀及單纖維之纖度〕 又，本發明之間位型全芳香族聚醯胺纖維之剖面形狀 ’可爲圓形、橢圓形、其他任意形狀，另外，單纖維之纖 度（單絲纖度）一般以0.5〜10. Odtex之範圍爲佳。 另外，本發明之間位型全芳香族聚醯胺纖維可由使用 具多數紡絲孔之紡絲抽絲口的濕式紡絲得到，例如每1抽 絲口得到1 〇 〇〜3 0，〇 〇 〇孔、得到2 〇 〇〜7 0,0 0 0 d t e X，較佳爲 -15- 201134993 1，000 〜20,000孔、得到 2,〇〇〇 〜45,000dtex之絲束。 〔間位型全芳香族聚醯胺之構成〕 構成本發明之間位型全芳香族聚醯胺纖維的間位型全 芳香族聚醯胺係由間位型芳香族二胺成分與間位型芳香族 二羧酸成分所構成者，在不損及本發明之目的範圍内，可 共聚合對位型等其他的共聚合成分。 本發明中尤其適宜使用者，由力學特性、耐熱性、難 燃性之觀點來看，爲以間位亞苯基異苯二甲醯胺（m-phenyleneisophthalamide )單元爲主成分之間位型全芳香 族聚醯胺。 由間位亞苯基異苯二甲醯胺單元所構成之間位型全芳 香族聚醯胺，間位亞苯莲異苯二甲醯胺單元以佔全重複單 元之9 0莫耳％以上爲佳’更佳爲9 5莫耳％以上、特別佳爲 1 00莫耳。 〔間位型全芳香族聚醯胺之原料〕 (間位型芳香族二胺成分） 間位型全芳香族聚醯胺之原料的間位型芳香族二胺成 分，例如間苯二胺、3,4’ -二胺基二苯基醚、3,4’ —二胺 基二苯基磺基等、及、於此等之芳香環具有鹵素、碳數i 〜3之烷基等取代基之衍生物’例如2,4 一二胺甲苯、2,6 一二胺甲苯、2,4 一二胺基氯苯、2,6 —二胺基氯苯等。其 中’以僅間苯二胺’或含間苯二胺8 5莫耳％以上、較佳爲 -16- 201134993 9〇莫耳％以上、特別佳爲95莫耳％以上之混合二胺爲佳。 (間位型芳香族二羧酸成分） 構成間位型全芳香族聚醯胺之間位型芳香族二羧酸成 分之原料’例如間位型芳香族二羧酸鹵化物。間位型芳香 族二羧酸鹵化物如異苯二甲酸氯化物、異苯二甲酸溴化物 等異苯二甲酸鹵化物、及於此等之芳香環具有鹵素 '碳數 1〜3烷氧基等取代基之衍生物，例如3 —氯異苯二甲酸氯 化物等。其中，以異苯二甲酸氯化物、或含異苯二甲酸氯 化物8 5莫耳％以上、較佳爲9 0莫耳％以上、特別佳爲9 5莫 耳％以上之混合羧酸鹵化物爲佳。 本發明之間位型全芳香族聚醯胺纖維實質上不含層狀 黏土礦物。所謂「實質上不含」係指製造間位型全芳香族 聚醯胺、以及間位型全芳香族聚醯胺纖維時，不刻意添加 層狀黏土礦物。濃度雖未特別限定，例如0.01質量％以下 ，較佳爲0.001質量％以下，更佳爲0.0001質量％以下。 〔間位型全芳香族聚醯胺之製造方法〕 間位型全芳香族聚醯胺之製造方法並未特別限定，例 如可藉由以間位型芳香族二胺成分與間位型芳香族二羧酸 氯化物成分爲原料之溶液聚合或界面聚合等製造。 又，本發明所使用之間位型全芳香族聚醯胺之分子量 爲可形成纖維程度即可，未特別限定。一般爲得到充分的 物性之纖維，以濃硫酸中、聚合物濃度lOOmg/lOOmL硫 -17- 201134993 酸下30°C所測定之固有黏度（I.V·)爲1.0〜3.0之範圍之 聚合物爲佳，1.2〜2.0之範園之聚合物特佳。 <間位型全芳香族聚醯胺纖維之製造方法> 本發明之間位型全芳香族聚醯胺纖維係使用以上述之 製造方法得到之芳香族聚醯胺，例如經以下說明之紡絲液 調製步驟、紡絲•凝固步驟、可塑延伸浴延伸步驟、洗淨 步驟、乾熱處理步驟、熱延伸步驟來製造。 〔紡絲液調製步驟〕 紡絲液調製步驟中，將間位型全芳香族聚醯胺溶於醯 胺系溶劑，調製紡絲液（間位型全芳香族聚醯胺聚合物溶 液）。紡絲液的調製中，一般使用醯胺系溶劑，所使用醯 胺系溶劑，如Ν _甲基一2 —吡咯烷酮（ΝΜΡ )、二甲基甲 醯胺（DMF )、二甲基乙醯胺（DMAc )等。此等中由溶 解性與操作安全性之觀點來看，以使用NMP或DM Ac爲佳 〇 溶液濃度由接下步驟的紡絲•凝固步驟的凝固速度及 聚合物之溶解性之觀點來看，適宜選擇適當濃度即可，例 如聚合物爲聚間苯二甲醯間苯二胺等之間位型全芳香族聚 醯胺且溶劑爲NMP等之醯胺系溶劑時’通常以〜30質量 %之範圍爲佳。 〔紡絲•凝固步驟〕 -18- 201134993 紡絲•凝固步驟中，將上述所得到之紡絲液（間位型 全芳香族聚醯胺聚合物溶液）於凝固液中紡出使凝固。 紡絲裝置未特別限定，可使用以往習知濕式紡絲裝置 。另外，可安定濕式紡絲者即可，不需特別限制紡絲抽絲 口之紡絲孔數、排列狀態、孔形狀等，例如可使用孔數 1，000〜30,000個、紡絲孔徑0.05〜〇.2mm之切段纖維用之 多孔紡絲抽絲口等。 另外，從紡絲抽絲口紡出時，紡絲液（間位型全芳香 族聚醯胺聚合物溶液）之溫度以20〜90 °C之範圍爲佳。 爲獲得本發明之纖維所用凝固浴，在浴液的溫度10〜 5〇°c之範圍使用實質上不含無機鹽之醯胺系溶劑、較佳爲 NMP的濃度爲45〜60質量％之水溶液。醯胺系溶劑（較佳 爲NMP )之濃度未達45質量％，則皮層成爲厚構造，於洗 淨步驟中洗淨效率降低，降低纖維之殘存溶劑量變困難。 另一方面，醯胺系溶劑（較佳爲NMP )之濃度超過60質量 %時，無法使至纖維内部爲止進行均一凝固，因此降低纖 維之殘存溶劑量變得困難。又，纖維浸漬於凝固浴中之時 間以0.1〜30秒之範圍爲佳。 在此，實質上不含鹽之凝固液，以實質上僅以醯胺系 溶劑與水構成者爲佳。然而，因氯化鈣、氫氧化鈣等無機 鹽類之後會由聚合物溶液中抽出，故實際上於凝固液含有 少量此等鹽類。工業上實施的鹽類之較佳濃度相對於凝固 液全體在0.3質量％〜10%質量之範圍。無機鹽濃度未達0.3 質量％則在凝固液的回收製程中精製用的回收花費明顯變 -19- 201134993 高而不宜。另一方面’無機鹽濃度超過10質量％時，凝固 速度變慢，從紡絲抽絲口吐出後之纖維立刻易於產生黏附 ’另外’因凝固時間變長，凝固設備不得不大型化而不佳 〇 本發明中’藉由將凝固浴之成分或條件如上述設定， 可使纖維表面形成之皮層變薄、至纖維内部爲止爲均一構 造，進而，可提升所得纖維之破斷伸度。 經該紡絲•凝固步驟，在凝固浴中形成由多孔質的間 位型全芳香族聚醯胺之凝固絲所成之纖維（絲束），之後 ，從凝固浴拉出至空氣中。 〔可塑延伸浴延伸步驟〕 可塑延伸浴延伸步驟中，以凝固浴凝固得到之纖維成 爲可塑狀態時，在可塑延伸浴中進行纖維延伸處理。 可塑延伸浴液並未特別限制，可使用以往習知者。 例如可使用由醯胺系溶劑的水溶液而成，實質上不含 鹽類之水溶液，工業上，以使用與上述凝固浴所用者同種 類之溶劑爲特佳。亦即，以與聚合物溶液、凝固浴及可塑 延伸浴所用醯胺系溶劑同種爲佳，以使用N -甲基- 2 -吡咯烷酮（NMP )之單獨溶劑、或含NMP之2種以上所成 之混合溶劑特佳。藉由使用同種的醯胺系溶劑，可將回收 步驟統合·簡略化，對經濟上有益。 可塑延伸浴溫度與組成各自有密切關係，但醯胺系溶 劑的質量濃度爲20〜70質量％、且溫度爲20〜70 °C之範圍 -20- 201134993 下則可適宜地使用。較該範圍低之領域，多孔質纖維狀物 之可塑化無法充分地進行，在可塑延伸要得到充分的延伸 倍率變得困難。另一方面，較此範圍高之領域，多孔質纖 維之表面溶解而黏附，良好製絲變得困難。 爲得到本發明之纖維，可塑延伸浴中之延伸倍率需要 在3.5〜10.0倍之範圍，更佳爲4.0〜6.5倍之範圍。本發明 中，藉由將可塑延伸浴中之延伸以該倍率之範圍進行，因 延伸提升分子鏈配向，可確保最後所得纖維之強度。 在可塑延伸浴中之延伸倍率未達3.5倍時，得到具 5.0cN/ dtex以上破裂強度之纖維變得困難。另一方面， 延伸倍率超過1 〇·〇倍時，因產生單絲斷裂，生產安定性惡 化。 可塑延伸浴的溫度以20〜90°C之範圍爲佳。溫度在20 〜90°C之範圍時，因步驟狀態佳，故較佳。上述溫度更佳 爲 2 0 〜6 0 〇C。 〔洗淨步驟〕 洗淨步驟中，將以可塑延伸浴延伸的纖維充分地洗淨 。洗淨對所得之纖維之品質面有影響，以多段進行爲佳。 尤其，洗淨步驟中洗淨浴的溫度及洗淨浴液中之醯胺系溶 劑的濃度影響著從纖維抽出醯胺系溶劑的狀態及來自洗淨 浴之水浸入纖維中之狀態。因此，在將此等最適化的目的 中，亦以將洗淨步驟多段化，並控制溫度條件及醯胺系溶 劑的濃度條件爲佳。 -21 - 201134993 關於溫度條件及醯胺系溶劑的濃度條件，爲最後 到品質滿意之纖維者即可，並不特別限制，但使最初 浴爲60°C以上之高溫，則水之向纖維中的浸入同時發 故於纖維中生成巨大空隙、招致品質劣化。因此，最 淨浴以3 (TC以下之低溫爲佳。 纖維中殘留溶劑時，在高溫下無法抑制纖維之著 變色（尤其黃變），另外，產生物性降低或收縮、限 指數（LOI )之降低等。因此，本發明之纖維所含有 劑量必須在1.0質量％以下，0.5質量％以下更佳。 〔乾熱處理步驟〕 爲得到本發明之纖維，對經上述洗淨步驟的纖維 爲施加乾熱處理步驟。乾熱處理步驟中，經上述洗淨 施加洗淨的纖維，較佳爲在1 0 0〜2 5 0 °C、更佳爲1 〇 〇 -°C之範圍進行乾燥熱處理。在此，乾熱處理雖未特別 ，以定長下爲佳。 洗淨步驟後，接著施加乾燥熱處理，可適度提升 物流動性、配向，抑制結晶化並促進纖維之緻密化。 上述乾熱處理的溫度係指熱板、加熱輥等之纖維加熱 之設定溫度。 〔熱延伸步驟〕 本發明中，對經上述乾熱處理步驟的纖維，施加 伸步驟。熱延伸步驟中，邊在310〜335 °C進行熱處理 可得 洗淨 生， 初洗 色或 界氧 之溶 較佳 步驟 ^ 200 限制 聚合 又， 手段 熱延 ，邊 -22- 201134993 進行1 · 1〜1 . 8倍的延伸。熱延伸步驟中熱處理溫度超過 3 3 5 °C之高溫時，絲著色，且激烈劣化、破裂強度降低， 因情況而有斷絲之情形。另一方面，低於3 1 0°C溫度，則 纖維之充分的結晶化無法達成，難以表現期望之纖維物性 亦即破裂強度等力學的特性及熱的特性。 熱延伸步驟中處理溫度與所得之纖維之密度有密切關 係。爲獲得特別良好纖維密度之製品，熱延伸步驟中熱處 理溫度以310〜335 °C之範圍爲佳。另外，藉由熱延伸步驟 中熱處理溫度在3 1 0〜3 3 5 °C之範圍，可得到3 0 0 °C乾熱收 縮率爲5.0 %以下之纖維。又，熱處理以乾熱處理特別佳， 熱延伸步驟中熱處理溫度爲熱板、加熱輥等之纖維加熱手 段之設定溫度。 另外，熱延伸步驟中延伸倍率與表現所得之纖維之強 度及彈性率密切相關。爲得到本發明之纖維，一般需要設 定於1.1〜1.8倍、較佳爲1.1〜1.5倍之範圍，在該範圍， 可維持良好熱延伸性且表現必要強度及彈性率》 <間位型全芳香族聚醯胺纖維之用途> 本發明之間位型全芳香族聚醯胺纖維，因應需要施加 捲縮加工等’且切斷爲適當纖維長，供應至紡織的其他次 步驟。 此外’本發明之間位型全芳香族聚醯胺纖維，可活用 其耐熱性、耐炎性、力學特性，應用於各種的用途。例如 將本發明之纖維單獨或與其他的纖維組合作成織編物，可 -23- 201134993 用作消防服、防護服等之耐熱耐炎衣料、耐炎性之寝具、 裝潢材料。另外’亦可有效作爲不織布、作爲過濾膜等之 各種工業材料'或作爲合成紙、複合材料之原料， 特別是本發明之間位型全芳香族聚醯胺纖維即使高溫 下之加工及使用’可維持高強度且抑制製品之著色或變色 。因此’特別可用於用於暴露在高溫狀況之用途，例如作 爲高溫用毛氈之基布、高溫氣體過濾膜等之素材或利用其 高彈性率而用作橡膠或樹脂等之基質補強材。 【實施方式】 [實施例] 以下，以實施例等將本發明具體說明，但本發明不限 於此等之實施例等。又，「份」及「％」不特別限定時係 指基於「質量」者，「量比」不特別限定時係指「質量比 」。進而，用於紡絲的聚合物溶液（紡絲原液）中聚合物 濃度（PN濃度）爲對於「全質量份」之「聚合物之質量％ J ，亦即，爲〔聚合物/ (聚合物+溶劑+其他）〕X1 00 (%)。 <測定方法> 實施例及比較例中各物性値使用下述方法測定。 〔固有黏度（IV)〕 從聚合物溶液純化出芳香族聚醯胺聚合物、乾燥後， -24- 201134993 濃硫酸中，以聚合物濃度iOOmg/lOOmL硫酸在30°C進行 測定。 〔單絲纖度〕 依據JIS L 1015，進行依據正量纖度之A法的測定， 以表觀纖度表記。 〔破裂強度、破斷伸度、初期彈性率〕 使用拉伸試驗機（Ins tron公司製、型式：5565)，依 據JIS L 1 0 1 5，使用以下之條件進行測定。 (測定條件） 抓取間隔 ：20mm 初荷重 ：0.044cN ( 1 / 20g ) / dtex 拉伸速度 ：20mm /分鐘 〔纖維中殘存之溶劑量（殘存溶劑量）〕 在洗淨步驟出口側採樣纖維，使該纖維在離心分離機 (轉數5,000rpm )離心1〇分鐘，測定此時的纖維質量（ Ml)。將該纖維於質量M2g之甲醇中進行4小時煮沸，抽 出纖維中之醯胺系溶劑及水。使抽出後之纖維在1 〇 5 t環 境下進行2小時乾燥，測定乾燥後之纖維質量（p )。另外 ’使抽出液中所含有之醯胺系溶劑的質量濃度（C )以氣 體層析法求出。 •25- 201134993 纖維中殘存之溶劑量（醯胺系溶劑質量）N ( % )爲 使用上述Ml、M2、P、及C，以下述式算出。 N = [C/100]x[(Ml+M2-P)/P]xl〇〇 〔300°C乾熱收縮率〕 在約3,300dtex之絲束上垂吊98cN(100g)之荷重， 相互在距離3 0cm處做記號。除去荷重後，將絲束放置於 3 00°C環境下、1 5分鐘後，測定記號間之長度L。將測定結 果L代入下述式所得之値爲3 0 0 °C乾熱收縮率（％ )。 3〇〇°C 乾熱收縮率（％) = [(30-L)/30]xl00 〔色相値（L * 一 b * )〕 對得到之纖維、及、25 0°C之乾燥機中進行1〇〇小時熱 處理後之纖維進行色相値之測定。具體上，使用彩色測色 裝置（Macbeth公司製、商品名：Macbeth COLOR — EYE 型號CE - 3 1 00 )，用以下之測定條件進行測定，求出色 相値（L * — b * )之變化。色相値（L * 一 b * )數値愈 小黃變愈顯著。又，L *、b *可經JIS Z 8 7 2 8 ( 1 〇度視野 XYZ系之色表示方法）規定之三刺激値求出。 (測定條件） 視野：1 0度 -26- 201134993 光源：D65 波長：360〜740nm <實施例1 > 〔紡絲原液（紡絲用原液）調製步驟〕 將依據特公昭47 - 1 08 63號公報記載之方法經界面聚 合法製造，固有黏度（IV )爲1.9之聚間苯二甲醯間苯二 胺粉末20·0份懸濁於冷卻至-10°C之N -甲基—2 —吡咯烷 酮（NMP) 80.0份中，成爲漿狀。接著將懸濁液升溫至60 °C，使溶解，而得到透明的聚合物溶液。 〔紡絲步驟〕 將得到之聚合物溶液作爲紡絲原液’由孔徑〇.〇7mm 、孔數1,5 00之紡絲抽絲口吐出於浴溫度4〇°C之凝固浴中 進行紡絲。凝固液的組成爲水/ NMP (量比）=45 / 5 5， 凝固浴中以絲速7m /分鐘進行紡絲。 〔可塑延伸步驟〕 接著，在溫度40°C之水/ NMP (量比）=40/ 60之組 成的可塑延伸浴中，以5.0倍的延伸倍率進行延伸。 〔洗淨步驟〕 延伸後，依序通過2(TC之水/ NMP (量比）=70/ 30 之浴（浸漬長1.8m)、繼而2(TC之水浴（浸漬長3·6χη)、 -27- 201134993 進而6 0 °C之溫水浴（浸漬長5 · 4m )，接著8 0 °C之溫水浴（ 浸漬長3.6 m )充分地進行洗淨。 〔乾燥熱處理步驟〕 洗淨後之纖維，接著以表面溫度15〇°C之熱輥在定長 下施加乾燥熱處理。 〔熱延伸步驟〕 接著以表面溫度33(TC之熱輥邊施加熱處理，邊施加 延伸爲1 · 3倍之熱延伸步驟，最後得到聚間苯二甲醯間苯 二胺纖維。 〔測定•評估〕 對得到之纖維（絲束）進行各種的測定評估。纖度爲 2.1dtex、破裂強度爲5.5cN/ dtex、破斷伸度爲24.0%，皆 爲良好數値。另外，纖維中之殘存溶劑量爲0.4%、300 °C 乾熱收縮率爲3.9%、初期彈性率爲l，250cN/ mm2，具優 異熱收縮安定性。得到之結果如表1。 <實施例2 > 紡絲原液（紡絲用原液）調製步驟中，除將使用之溶 劑變更爲N，N —二甲基乙醯胺（DMAe )製造聚合物溶液 ，將此用於紡絲原液以外，與實施例1同樣地製作聚間苯 二甲醯間苯二胺纖維。對得到之纖維進行各種測定結果如 -28 - 201134993 表1。 <比較例1 > 凝固步驟中，除將凝固液的組成變更爲水/ NMP (量 比）=7 〇 / 3 0以外，與實施例1同樣地’製造聚間苯二甲 醯間苯二胺纖維。得到之纖維的各種測定結果如表1 <比較例2 > 除將熱延伸步驟中延伸倍率變更爲1 · 〇倍以外，與實 施例1同樣地得到聚間苯二甲醯間苯二胺纖維。得到之纖 維的各種測定結果如表1。 <實施例3 > 〔紡絲原液（紡絲用原液）調製步驟〕 在乾燥氮環境下之反應容器中，秤量水分率lOOppm 以下之NMP 721.5份’於該NMP中溶解間苯二胺97.2份（ 5 〇 · 1 8莫耳％ ) ’冷卻至〇 °c。於該經冷卻之n Μ P溶液進一 步緩緩攪拌添加異苯二甲酸氯化物（以下簡稱IPC) 181.3 份（4 9 · 8 2莫耳％)，進行聚合反應。又，黏度變化停止後 ，繼續攪拌4〇分鐘，使聚合反應完畢。 接著’稱量平均粒徑lOym以下之氫氧化鈣粉末66.6 份’對聚合反應完畢之聚合物溶液緩慢添加，進行中和反 應。氫氧化鈣投入完畢後’再攪拌4 〇分鐘，而得到透明的 聚合物溶液。 -29- 201134993 從得到之聚合物溶液純化聚間苯二甲醯間苯二胺後測 定IV爲1 · 2 5 »另外，聚合物溶液中之聚合物濃度爲2 〇 %。 〔紡絲步驟·可塑延伸步驟•多段洗淨步驟·乾燥熱 處理步驟·熱延伸步驟〕 將得到之聚合物溶液作爲紡絲原液，使紡絲步驟中絲 速爲5m/分鐘，可塑延伸步驟中可塑延伸浴中之延伸倍 率爲6.5倍以外，與實施例1同樣地，得到聚間苯二甲醯間 苯二胺纖維。對得到之纖維進行各種測定結果如表1。 <實施例4 > 紡絲原液（紡絲用原液）調製步驟中，將使用之溶劑 變更爲N，N —二甲基乙醯胺（DM Ac )以外，與實施例3同 樣地，製造聚合物溶液，將得到之聚合物溶液作爲紡絲原 液，與實施例1同樣地，得到聚間苯二甲醯間苯二胺纖維 。對得到之纖維進行各種測定結果如表1。 <比較例3 > 將凝固步驟中’凝固液的組成變更爲水/ NMP (量比 )=3 0 / 70以外’與實施例3同樣地，得到聚間苯二甲醯 間苯二胺纖維。對得到之纖維進行各種測定結果如表1 ^ <比較例4〜5 > 將熱延伸步驟中延伸倍率變更爲1 . 〇倍以外，各自與 -30- 201134993 間苯二胺纖 實施例3及實施例4同樣地，得到聚間苯二甲醯 維。對得到之纖維進行各種測定結果如表1。 -31 - 201134993 【i】 比較例5 DMAc 45/55 vn vd 330 p <N CN ON (N 20.5 fO d 00 (N Ο VD 77.8 73.7 比較例4 NMP 45/55 in vd 330 q iS 卜 <n 18.0 d 卜 <N 710 78.3 1 75.8 比較例3 NMP 30/70 vd os CNi 35.0 <N Ό o v〇 71.1 66.2 比較例2 NMP 45/55 o … 330 Ο CN (N 卜 rn 28.5 On 〇 心 CO o 卜 78.5 76.3 丨比較例1 NMP 70/30 o 330 ΓΛ 〇 ΓΟ 14.0 <N oo 72.1 67.6 j實施例4 DMAc 45/55 vd 330 fO (N r^i 00 wS 18.9 0.08 v〇 rn 1 1180 78.9 77.7 實施例3 NMP 45/55 VO rn 口 o 18,5 d On 1170 79.0 j 78.5 實施例2 DMAc 45/55 O vri 330 (N r4 卜 wS 20.5 (N d oo CN 990 79.5 77.8 實施例1 NMP 1 i 45/55 o 330 ro wS 24.0 寸 ό ON rn 1250 1 79.7 ! 77.1 聚合物溶解醯胺系溶劑 凝固浴醯胺系溶劑組成(水/溶劑） § s Ρ m (dtex) (cN/dtex) g Vw/ /—V (cN/mm2) 熱處理前 色相（L * -b *) 250°C熱處理後 色相（L*-b*) 可塑延伸倍率 熱延伸溫度 熱延伸倍率 纖度 破裂強度 破斷伸度 殘存溶劑量 300°C乾熱收縮率 初期彈性率 -32- 201134993 [產業上利用性] 根據本發明，可提供力學特性、耐熱性等 中殘存之溶劑極微量而實質上不含層狀黏土礦 全芳香族聚醯胺纖維（尤其，聚間苯二甲醯間 維）。因此，使用本發明之間位型全芳香族聚 纖維製品即使在高溫下之加工及使用條件下， 、抑制著色或變色。因此，本發明之間位型全 胺纖維尤其在高溫下加工或使用之領域有用。 良好且纖維 物之間位型 苯二胺系纖 醯胺纖維的 可維持強度 芳香族聚醯 -33-201134993 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to meta-type wholly aromatic polyamide fibers. More specifically, it relates to a novel meta-type wholly aromatic polyamide fiber which can be obtained without a layered clay mineral, which is excellent in mechanical properties and high in quality. [Prior Art] The wholly aromatic aromatic polyamide produced from an aromatic diamine and an aromatic dicarboxylic acid dichloride is excellent in heat resistance and excellent in flame retardancy. In addition, these wholly aromatic polyamines are soluble in the amide-based solvent, and thus the polymer solution can be obtained by dry spinning, wet spinning, semi-dry semi-wet spinning, or the like. Known for it. Among the wholly aromatic polyamines, polymetaphenyl ene-isophthalamide represents a meta-type wholly aromatic polyamine (hereinafter referred to as "meta-aromatic polyamine"). Fibers can be used as heat-resistant and flame-retardant fibers. For the method of intercalating aromatic polyamine fibers, the following two methods (a) and (b) can be used. Further, the method for producing the meta-aramid fiber of the present invention is also proposed in the method of (c) to (e). (a) preparing a poly(m-xylylenediphenyl) m-phenylenediamine solution by low-temperature solution polymerization of m-phenylenediamine and isophthalic acid chloride in ν, Ν-dimethylacetamide, after which A method for producing a meta-aromatic polyamine fiber by dry-spinning a obtained polymer solution by neutralizing the hydrochloric acid produced by the by-product in the solution with calcium hydroxide to obtain a calcium chloride-containing polymer solution.专用-5- 201134993 Li Wen 1: Special Gong Zhao 3 5 - 1 4399 Bulletin]. (b) an organic solvent system (for example, tetrahydrofuran) and a mineral acid-accepting agent and an aqueous solution containing a soluble neutral salt, which are a good solvent for a non-polymerized polyamine containing a meta-phenylenediamine salt and an isophthalic acid chloride. The powder of the poly(m-xylylenediphenyl) m-phenylenediamine polymer is separated by contact (Patent Document 2, Japanese Patent Publication No. 47-1768), and the polymer powder is redissolved in the amide-based solvent. A method of wet spinning in an aqueous coagulation bath containing an inorganic salt (Patent Document 3: Japanese Patent Publication No. Hei. No. Hei. No. Hei. (c) The meta-position of a non-inorganic salt or a trace amount (2 to 3%) of lithium chloride dissolved in a guanamine-based solvent by a solution polymerization method. A method of producing a molded article of a fiber or the like by a wet molding method of an aromatic polyamine solution (Patent Document 4: JP-A-50-52 1 67). (d) solution polymerization in a guanamine solvent, and a meta-aromatic polyamine polymer solution containing calcium chloride and water formed by neutralization with calcium hydroxide, calcium oxide or the like is pressed into the gas from the pores. After passing through the gas, it is introduced into an aqueous coagulation bath, and then a method of forming a fibrous material by passing through an aqueous solution of an inorganic salt such as calcium chloride (Patent Document 5: JP-A-56-311). (e) a solution of an aromatic polyamine polymer solution containing calcium chloride and water formed by solution polymerization in a guanamine solvent and neutralized with calcium hydroxide, calcium oxide or the like and spun from the pores A method of forming a fibrous material in an aqueous coagulation bath containing a high concentration of calcium chloride (Patent Document 6: JP-A-8-074 1 2, Patent Document 7: JP-A-8-8421, etc. 201134993 Since the method (a) above is dry spinning, the fibrous polymer solution spun from the spinning wire is volatilized and dried from the surface of the formed fibrous material to form a dense and fibrous surface. Therefore, even if the fibrous material is continuously washed with water or the like, it is difficult to sufficiently remove the residual solvent. Further, the fiber obtained by the method (a) is in a high temperature environment due to the solvent remaining in the fiber. Yellowing occurs during use. Therefore, heat treatment at a high temperature must be avoided, and as a result, there is a problem that it is difficult to increase the strength. On the other hand, since the methods (b) to (e) above are wet spinning, the spinning stage solvent Non-volatile However, when a fibrous polymer is introduced into an aqueous coagulation bath containing an aqueous coagulation bath or a high concentration inorganic salt, the solvent is separated from the vicinity of the surface of the fibrous polymer into the aqueous coagulation bath, and the water contained in the coagulation bath is The surface of the solidified fibrous material is immersed in the vicinity of the fibrous material to form a strong sheath layer. Therefore, the fiber obtained by the dry spinning method is also difficult to sufficiently remove the solvent remaining in the fiber, and the residual solvent cannot be avoided. Coloring or discoloration (especially yellowing) in a high-temperature environment. Therefore, even in the case of the fibers obtained by the methods (b) to (e), it is necessary to avoid high-temperature heat treatment, and it is difficult to increase the strength of the fibers. In the case of coagulating a meta-aromatic polyamine solution into a porous fibrous material, it may be in a state in which the porous contains a coagulating liquid, or in the porous state, in the document 8 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. a method of heating a fiber containing a moldable liquid, heating it in the air, and then heating it in a state containing the coagulating liquid or the like, followed by heat treatment According to the method described in Patent Document 8, when the meta-aramid solution is solidified into a fibrous material, the surface becomes a porous fibrous material having no sheath layer. However, the plastic-containing liquid is contained. When the porous fibrous material is heated, it becomes difficult to remove the solvent, and as a result, the fiber obtained by the method cannot avoid coloring or discoloration (especially yellowing) in a high temperature environment caused by the residual solvent. The fiber obtained by the method described in Patent Document 8 is required to avoid high-temperature heat treatment and has a problem that it is difficult to increase the strength of the fiber. Patent Document 9 and Patent Document 10 disclose a wholly aromatic poly group containing a layered clay mineral. Amidoxime fiber. Patent Document 9 and Patent Document 10 describe that a meta-type wholly aromatic polyamide fiber is blended with a layered clay mineral to form a fiber having a low residual solvent amount. However, the in-line wholly aromatic polyamine fibers containing these layered clay minerals have the characteristics of low-level insulation, and thus the layered clay minerals during cutting or twisting processing. The situation of falling off and scattering. Therefore, further improvement is sought from the viewpoint of improving the insulation or preventing the layered clay mineral from falling off and scattering. - Patent Document 1 1 describes a high-temperature processing in which the amount of solvent remaining in the fiber is 1.0% by weight or less, the dry heat shrinkage ratio at 300 °C is 3% or less, and the fiber breaking strength is 3.0 cN/dtex or more. Sexually preferred inter-type aromatic polyamide fibers. However, Patent Document 11 does not describe fibers having a breaking strength of 4.5 cN/dtex or more, and is intended to improve the high breaking strength and dimensional stability sought for base fabric applications or rubber reinforcing applications of high-temperature films. [Prior Art Document] -8-201134993 [Patent Document] [Patent Document] Japanese Patent Publication No. Sho. No. Sho. No. Sho. No. Sho. [Patent Document 5] JP-A-56-31-9 (Patent Document 6) JP-A-H08-074121 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The present invention has been made in view of the above-described prior art, and an object thereof is to provide a meta-type such as heat resistance and flame retardancy. The novel aromatic polybenzamine fibers have a novel inter-type wholly aromatic polyamide fiber which has the properties of high breaking strength and can suppress coloration or discoloration at high temperatures. [Means for Solving the Problem] The present inventors have made an effort to solve the above problems. As a result, it has been found that by appropriately adjusting the composition or condition of the coagulation bath which is a dense solidified form having no sheath core, and performing plastic extension in a range of a specific magnification, the heat extension condition after appropriately adjusting -9 - 201134993 can solve the above. The subject matter is completed and the present invention has been completed. That is, the present invention is a meta-type wholly aromatic polyamide fiber substantially free of layered clay mineral, and the amount of solvent remaining in the fiber is 1.0% by mass or less relative to the entire fiber, and the fiber burst strength It is a meta-type wholly aromatic polyamide fiber of 4.5 to 6.0 cN / dtex. Here, the meta-type wholly aromatic polyamide fiber of the present invention preferably has a dry heat shrinkage ratio of 3.0% or less at 300 °C. Further, the meta-type wholly aromatic polyamide fiber of the present invention preferably has an initial elastic modulus of 800 to 1, 500 cN / mm 2 . [Effect of the Invention] According to the present invention, it is possible to provide a solvent which is excellent in mechanical properties, heat resistance, and the like, and which is extremely small in the fiber and substantially free of a layer-type wholly aromatic polyamide fiber between layered clay minerals (especially, poly Benzoquinone m-phenylenediamine fiber). The fiber of the present invention has the strength originally possessed by the positional all-aromatic polyamide fiber in addition to heat resistance or flame retardancy, and can suppress the coloring or discoloration of the fiber or the fiber product during processing and use at a high temperature. (especially yellowing). Therefore, the fiber of the present invention can be used in the field where the conventional meta-type wholly aromatic polyamide fiber cannot be used, and the industrial price is extremely high [the best mode for carrying out the invention] <Meta-type wholly aromatic polyamide fiber> -10- 201134993 The meta-type wholly aromatic polyamide fiber of the present invention has the following specific physical properties. The physical properties, constitution, and production method of the meta-type wholly aromatic polyamide fiber of the present invention will be described below. [Physical properties of meta-type wholly aromatic polyamide fibers] The meta-type wholly aromatic polyamide fibers of the present invention have a breaking strength within a certain range and a very small amount of residual solvent in the fibers. Specifically, it is a meta-type wholly aromatic polyamide fiber which does not contain a layered clay mineral, and the residual solvent amount in the fiber is 1.0% by mass or less and the fiber has a burst strength of 4.5 to 6.0 cN/dtex. Therefore, the meta-type wholly aromatic polyamide fiber of the present invention can suppress the coloration or discoloration of fibers or articles even when processed and used at a high temperature. [Amount of Residual Solvent] Since the meta-type wholly aromatic polyamide fiber is generally produced by dissolving a polymer in a spinning dope of a guanamine solvent, it is a matter of course that a solvent remains in the fiber. However, in the meta-type wholly aromatic polyamide fiber of the present invention, the amount of the solvent remaining in the fiber is not more than 5% by mass based on the mass of the fiber. It must be below 1. 〇 mass%, at 0.5 mass. /. The following is better. Particularly preferably 0.01 to 0 · 1% by mass. When the solvent is more than 1. 〇 mass% of the solvent remaining in the fiber, when it is processed or used in a high temperature environment of more than 20 TC, it is easy to yellow, and the apparent strength is lowered, so that it is not preferable in the present invention. Residual -11 - 201134993 in the meta-type wholly aromatic polyamide fiber is in a range of 1. 〇 mass% or less. The plastic stretching is carried out within a specific magnification, and further, the thermal elongation condition after the adjustment is performed. In the present invention, the "amount of solvent remaining in the fiber" means a hydrazine obtained by the following method. (Method for measuring the amount of residual solvent) The fiber is sampled at the outlet side of the washing step, and the fiber is centrifuged (revolution number) 1500 rPm) was centrifuged for 1 minute, and the fiber mass (Ml) at this time was measured. The fiber was boiled in methanol of mass M2g for 4 hours, and the amide-based solvent and water in the fiber were extracted, and the fiber after extraction was taken at 05. The fiber mass (P) after drying was measured for 2 hours in a ° C environment, and the mass concentration (C) of the guanamine-based solvent contained in the extract was determined by gas chromatography. Solvent The amount (the amide type solvent mass) N (%) is calculated by the following formula using the above M1, M2, P, and C. N = [C/100]x [(Ml+M2-P)/P]xl〇 〇 [breaking strength] The inter-type wholly aromatic polyamide fiber of the present invention has a burst strength of 4.5 to 6.0 cN/dtex. It must be in the range of 4.5 to 6.0 cN/dtex 'to 5.5 to 6_0 〇> The range of 1/{^\ is preferably. More preferably, it is in the range of 5.7 to 6.0 cN/dtex, and further preferably in the range of 5.8 to 6.0 cN/dtex. The strength of the product is less than 4.5 cN/dtex. Low, no "12- 201134993 is not suitable for use in product applications. On the other hand, when it exceeds 6.0 cN/dtex, the elongation is greatly reduced, resulting in problems such as difficulty in operation of the product. In the wholly aromatic polyamide fiber, in order to set the "breaking strength" within the above range, the composition or condition of the coagulation bath is appropriately adjusted to form a dense solidified form having no sheath core, and the plastic stretching is performed within a specific ratio. In the present invention, the "breaking strength" is determined according to JIS L 1015. The machine was measured by the following conditions using Instron, model 5 565. (Measurement conditions) Grab interval: 20 mm Initial load: 0.044 cN (l/20 g) / dtex Tensile speed: 20 mm/min [broken Elongation at break The inter-type wholly aromatic polyamide fiber of the present invention preferably has a breaking elongation of 15% or more and more preferably 18% or more, and more preferably 20% or more. When the breaking elongation is less than 1 5%, the passability of the step is lowered in the post-processing step such as textiles, which is not preferable. In the present invention, the "breaking elongation" of the meta-type wholly aromatic polyamide fiber is controllable in the solidification step of the production method described later by the dense solidification form without the sheath core. In order to make it 15% or more, the coagulating liquid is made into a solution of a guanamine-based solvent, for example, Ν Μ P (N-methyl-2-pyrrolidone) at a concentration of 45 to 60% by mass, and the bath temperature becomes 10 ~5〇°c can be. Further, "breaking elongation" herein refers to the basis of IIS L 1015, which is measured under the above-mentioned "rupture strength" measurement conditions. [300 °C dry heat shrinkage ratio] Further, in the meta-type wholly aromatic polyamide fiber of the present invention, 30 (TC dry heat shrinkage ratio is preferably 5.0% or less, more preferably 1.0 to 4.0%). ° (When the dry heat shrinkage rate is large, the formed fiber structure shrinks at a high temperature to cause shrinkage of the fiber, and the design of the fiber structure becomes difficult. The dry heat shrinkage ratio is particularly preferably about 0.1 to 3%. In the meta-type wholly aromatic polyamide fiber, in order to make the dry heat shrinkage ratio of the above 3 ° C to 5.0% or less, in the production method described later, the heat treatment temperature in the heat extension step may be 3 1 0 to 3 3 In the range of 5 ° C. The dry heat shrinkage rate becomes larger at less than 3 10 ° C, and the strength is lowered and colored due to thermal deterioration of the polymer when it is higher than 3 3 5 ° C. Further, in the present invention, "300 °" C dry heat shrinkage rate refers to the enthalpy obtained by the following method. (Measurement method of dry heat shrinkage rate at 300 °C) Hanging load of 98cN (l〇〇g) on a bundle of about 3,300 dtex, mutual Make a mark at a distance of 30cm. After removing the load, place the tow in 30 (after TC environment, after 15 minutes) Degree L. Substituting the measurement result L into the following formula to obtain a dry heat shrinkage ratio (%) of 300 ° C ^ "14- 201134993 300 ° C dry heat shrinkage rate (%) = [(30-L) / 30] xl00 [initial elastic modulus] Further, the present invention is a meta-type wholly aromatic polyamide fiber having an initial modulus of elasticity of 800 〜 l, 500 cN/mm 2 , preferably 900 Å, and a range of 500 00 cN/mm 2 . When the initial elastic modulus is in the range of 800 to 1,500 cN / mm 2 , the formed fiber structure is less likely to be deformed by an external force, and it is easy to ensure dimensional accuracy when used for a base fabric of a nonwoven fabric or the like. In the amide fiber, in order to make the initial elastic modulus of 8 00 to 1, 500 cN/mm 2 , plastic extension can be applied in a plastic extension step of a production method to be described later in a range of 3 · 5 to 1 0.0 times. The stretching ratio is not reached. At the time of 3·5 times, the initial elastic modulus is not reached. On the other hand, when the ratio is higher than 1〇.〇, the yarn breaks easily, and the smoothness of the step is deteriorated. Here, the “initial elastic modulus” is based on JIS L. 1015, measured by the above-mentioned "breaking strength" measurement conditions. [Profile shape and fiber of single fiber且 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Further, the meta-type wholly aromatic polyamide fiber of the present invention can be obtained by wet spinning using a spinning wire having a plurality of spinning holes, for example, 1 Å per 1 wire drawing port. ~3 0, boring, get 2 〇〇~7 0,0 0 0 dte X, preferably -15- 201134993 1,000 ~ 20,000 holes, get 2, 〇〇〇 ~ 45,000 dtex tow. [Configuration of meta-type wholly aromatic polyamine] The meta-type wholly aromatic polyamine which constitutes the meta-type wholly aromatic polyamide fiber of the present invention is composed of a meta-type aromatic diamine component and a meta position. The constituent of the aromatic dicarboxylic acid component may copolymerize other copolymerized components such as a para-type within a range not impairing the object of the present invention. Particularly suitable for the user in the present invention, from the viewpoints of mechanical properties, heat resistance and flame retardancy, the m-phenylene isophthalamide unit is mainly composed of a meta-type. Aromatic polyamine. a meta-type wholly aromatic polyamine composed of meta-phenylene isophthalamide units, meta-phenylene isophthalamide units accounting for more than 90% of total repeat units It is better to be more than 9 5 mol%, and particularly preferably 100 mu. [Material of meta-type wholly aromatic polyamine] (meta-type aromatic diamine component) A meta-type aromatic diamine component of a raw material of a meta-type wholly aromatic polyamine, such as m-phenylenediamine, a substituent such as a 3,4'-diaminodiphenyl ether, a 3,4'-diaminodiphenylsulfonyl group, or the like, wherein the aromatic ring has a halogen, an alkyl group having a carbon number of i to 3, and the like Derivatives such as 2,4-diaminotoluene, 2,6-diamine toluene, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene, and the like. Among them, it is preferred to use a mixed diamine having only m-phenylenediamine or a m-phenylenediamine of 85 mol% or more, preferably 16-201134993 9 〇 mol% or more, particularly preferably 95 mol% or more. . (meta-type aromatic dicarboxylic acid component) A raw material constituting a meta-type wholly aromatic polyamine-based meta-type aromatic dicarboxylic acid component, for example, a meta-type aromatic dicarboxylic acid halide. a meta-type aromatic dicarboxylic acid halide such as an isophthalic acid chloride such as an isophthalic acid chloride or an isophthalic acid bromide, and an aromatic ring having a halogen 'carbon number 1 to 3 alkoxy group A derivative of an equivalent substituent such as 3-chloroisophthalic acid chloride or the like. Wherein, the mixed carboxylic acid halide is an isophthalic acid chloride or a polyoxyphthalic acid chloride containing 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more. It is better. The meta-type wholly aromatic polyamide fibers of the present invention are substantially free of layered clay minerals. The term "substantially free" refers to the undesired addition of layered clay minerals when producing meta-type wholly aromatic polyamines and meta-type wholly aromatic polyamide fibers. The concentration is not particularly limited, and is, for example, 0.01% by mass or less, preferably 0.001% by mass or less, and more preferably 0.0001% by mass or less. [Method for Producing Meta-Type All-Aromatic Polyamide] The method for producing the meta-type wholly aromatic polyamine is not particularly limited, and examples thereof include a meta-type aromatic diamine component and a meta-type aromatic The dicarboxylic acid chloride component is produced by solution polymerization or interfacial polymerization of a raw material. Further, the molecular weight of the meta-type wholly aromatic polyamine used in the present invention is not particularly limited as long as it has a molecular weight. Generally, in order to obtain sufficient physical properties, it is preferred to use a polymer having a concentration of intrinsic viscosity (IV·) of from 1.0 to 3.0 in concentrated sulfuric acid at a polymer concentration of 100 mg/lOOmL of sulfur-17-201134993 acid at 30 ° C. The polymer of 1.2 to 2.0 is very good. <Production Method of Meta-Type Fully Aromatic Polyamide Fiber> The meta-type wholly aromatic polyamide fiber of the present invention is an aromatic polyamine obtained by the above-described production method, for example, as described below. The spinning solution preparation step, the spinning and solidifying step, the plastic stretching bath extension step, the washing step, the dry heat treatment step, and the heat stretching step are carried out. [Spinning liquid preparation step] In the spinning solution preparation step, a meta-type wholly aromatic polyamine is dissolved in an amide-based solvent to prepare a spinning solution (meta-type wholly aromatic polyamine polymer solution). In the preparation of the spinning solution, a guanamine solvent is generally used, and a guanamine solvent such as Ν-methyl-2-pyrrolidone (ΝΜΡ), dimethylformamide (DMF), or dimethylacetamide is used. (DMAc) and so on. From the viewpoints of solubility and handling safety, the use of NMP or DM Ac is preferably the concentration of the solution from the viewpoint of the solidification rate of the spinning and solidification step of the subsequent step and the solubility of the polymer. It is sufficient to select an appropriate concentration. For example, when the polymer is a meta-type wholly aromatic polyamine such as poly(m-xylylene s-m-phenylenediamine) and the solvent is an amide-based solvent such as NMP, it is usually ～30% by mass. The range is good. [Spinning and solidification step] -18- 201134993 In the spinning and solidifying step, the spinning solution (meta-type wholly aromatic polyamine polymer solution) obtained above is spun in a coagulating liquid to be solidified. The spinning device is not particularly limited, and a conventional wet spinning device can be used. In addition, the wet spinning can be stabilized, and the number of spinning holes, the arrangement state, the hole shape, and the like of the spinning wire opening are not particularly limited. For example, the number of holes can be 1,000 to 30,000, and the spinning diameter is 0.05. ~ 〇. 2mm segmented fiber for the porous spinning wire drawing and so on. Further, when spinning from the spinning dope, the temperature of the spinning solution (meta-type wholly aromatic polyamine polymer solution) is preferably in the range of 20 to 90 °C. In order to obtain the coagulation bath for the fiber of the present invention, an aqueous solution of a guanamine-based solvent which does not substantially contain an inorganic salt, preferably a concentration of NMP of 45 to 60% by mass, is used in the range of the temperature of the bath at 10 to 5 ° C. . When the concentration of the guanamine-based solvent (preferably NMP) is less than 45% by mass, the skin layer has a thick structure, and the cleaning efficiency is lowered in the washing step, and it is difficult to reduce the amount of residual solvent of the fiber. On the other hand, when the concentration of the guanamine-based solvent (preferably NMP) exceeds 60% by mass, uniform solidification cannot be performed until the inside of the fiber, and therefore it is difficult to reduce the amount of residual solvent in the fiber. Further, the time during which the fibers are immersed in the coagulation bath is preferably in the range of 0.1 to 30 seconds. Here, the coagulating liquid substantially free of salt is preferably composed of substantially only a guanamine-based solvent and water. However, since inorganic salts such as calcium chloride and calcium hydroxide are later extracted from the polymer solution, a small amount of these salts are actually contained in the coagulation liquid. The preferred concentration of the salt to be industrially produced is in the range of 0.3% by mass to 10% by mass based on the entire solidified liquid. If the concentration of the inorganic salt is less than 0.3% by mass, the recovery cost for purification in the coagulating liquid recovery process is significantly changed. -19- 201134993 High is not suitable. On the other hand, when the inorganic salt concentration exceeds 10% by mass, the solidification rate becomes slow, and the fibers which are discharged from the spinning wire-drawing opening are liable to cause sticking immediately. In addition, since the solidification time becomes long, the solidification equipment has to be enlarged. In the present invention, by setting the components or conditions of the coagulation bath as described above, the skin layer formed on the surface of the fiber can be made thinner and has a uniform structure to the inside of the fiber, and the breaking elongation of the obtained fiber can be improved. Through the spinning and solidifying step, fibers (tows) made of a coagulated filament of a porous meta-type wholly aromatic polyamine are formed in a coagulation bath, and then pulled out from the coagulation bath into the air. [plastic extension bath extension step] In the plastic extension bath extension step, when the fiber obtained by solidification of the coagulation bath is in a plastic state, the fiber extension treatment is carried out in a plastic extension bath. The plastic extension bath is not particularly limited, and conventional ones can be used. For example, an aqueous solution of a guanamine-based solvent can be used, and substantially no salt aqueous solution is used. Industrially, it is particularly preferable to use a solvent similar to those used in the above-mentioned coagulation bath. That is, it is preferably the same as the amide-based solvent used in the polymer solution, the coagulation bath, and the plastic extension bath, and the N-methyl-2-pyrrolidone (NMP) alone solvent or NMP-containing two or more kinds are used. The mixed solvent is particularly good. By using the same amide-based solvent, the recovery step can be integrated and simplified, which is economically beneficial. The temperature of the plastic stretching bath is closely related to the composition, but the mass concentration of the amide solvent is 20 to 70% by mass, and the temperature is in the range of 20 to 70 ° C. -20 - 201134993 can be suitably used. In the field lower than this range, the plasticization of the porous fibrous material cannot be sufficiently performed, and it is difficult to obtain a sufficient stretching ratio in the plastic extension. On the other hand, in the field where the range is high, the surface of the porous fiber is dissolved and adhered, and it becomes difficult to form the wire well. In order to obtain the fiber of the present invention, the stretching ratio in the plastic stretching bath needs to be in the range of 3.5 to 10.0 times, more preferably in the range of 4.0 to 6.5 times. In the present invention, by extending the extension in the moldable stretching bath in the range of the magnification, the strength of the finally obtained fiber can be ensured by extending the molecular chain alignment. When the stretching ratio in the plastic stretching bath is less than 3.5 times, it becomes difficult to obtain a fiber having a breaking strength of 5.0 cN/dtex or more. On the other hand, when the stretching ratio exceeds 1 〇·〇, the production stability is deteriorated due to the occurrence of monofilament fracture. The temperature of the plastic stretching bath is preferably in the range of 20 to 90 °C. When the temperature is in the range of 20 to 90 ° C, it is preferable because the step state is good. The above temperature is more preferably 2 0 to 6 0 〇C. [Washing Step] In the washing step, the fibers extending in the moldable stretching bath are sufficiently washed. Washing has an effect on the quality of the resulting fiber, preferably in multiple stages. In particular, the temperature of the washing bath in the washing step and the concentration of the guanamine-based solvent in the washing bath affect the state in which the amide-based solvent is extracted from the fiber and the state in which the water from the washing bath is immersed in the fiber. Therefore, in the purpose of optimizing these, it is preferable to multiply the washing step and control the temperature conditions and the concentration conditions of the guanamine-based solvent. -21 - 201134993 The temperature conditions and the concentration of the guanamine-based solvent are not particularly limited as long as the fiber is satisfactory to the final quality. However, if the initial bath is at a high temperature of 60 ° C or higher, the water is directed into the fiber. At the same time, the immersion causes a large gap in the fiber to cause deterioration in quality. Therefore, the cleanest bath is preferably 3 (the low temperature below TC is preferred. When the solvent remains in the fiber, the discoloration (especially yellowing) of the fiber cannot be suppressed at a high temperature, and the physical property is lowered or contracted, and the limit index (LOI) is generated. Therefore, the fiber of the present invention must have a dose of 1.0% by mass or less and 0.5% by mass or less. [Dry heat treatment step] In order to obtain the fiber of the present invention, the fiber subjected to the above washing step is subjected to dry heat treatment. In the dry heat treatment step, the washed fibers are applied by the above washing, preferably in a range of from 1 to 10 ° C ° C, more preferably from 1 ° C to ° C. Here, dry Although the heat treatment is not particularly specific, it is preferably a fixed length. After the washing step, followed by applying a drying heat treatment, the fluidity and alignment of the material can be appropriately increased, the crystallization can be suppressed, and the densification of the fiber can be promoted. The temperature of the dry heat treatment refers to a hot plate. The set temperature of the fiber heating by the heating roller, etc. [The heat extension step] In the present invention, the fiber is subjected to the stretching step by the dry heat treatment step. In the heat stretching step, the edge is at 310~ The heat treatment at 335 °C can be used to obtain the washing, the initial washing or the dissolution of the boundary oxygen. The step 200 is limited to polymerization, and the method is heat-expanded. Side-22-201134993 performs 1 · 1~1 . 8 times extension. In the elongation step, when the heat treatment temperature exceeds the high temperature of 3 3 5 ° C, the filament is colored, and the filament is drastically deteriorated, the fracture strength is lowered, and the yarn is broken due to the situation. On the other hand, the fiber is lower than the temperature of 3 10 ° C. The sufficient crystallization cannot be achieved, and it is difficult to express the desired mechanical properties such as mechanical properties and thermal properties such as the breaking strength. The processing temperature in the thermal stretching step is closely related to the density of the obtained fiber. To obtain a particularly good fiber density. In the product, the heat treatment temperature in the heat extension step is preferably in the range of 310 to 335 ° C. Further, by the heat treatment temperature in the heat extension step, the temperature is in the range of 3 1 0 to 3 3 5 ° C, and 300 ° C is obtained. The heat shrinkage rate is 5.0% or less. Further, the heat treatment is particularly preferably a dry heat treatment, and the heat treatment temperature in the heat extension step is a set temperature of a fiber heating means such as a hot plate or a heating roll. The medium stretching ratio is closely related to the strength and elastic modulus of the fiber obtained. In order to obtain the fiber of the present invention, it is generally required to set the range of 1.1 to 1.8 times, preferably 1.1 to 1.5 times, in which good heat can be maintained. Extensibility and performance of necessary strength and elasticity <Use of meta-type wholly aromatic polyamide fiber> The meta-type wholly aromatic polyamide fiber of the present invention is subjected to crimping or the like as needed, and is cut into a suitable fiber length to be supplied to the textile. The other substeps. Further, the meta-type wholly aromatic polyamide fiber of the present invention can be used in various applications by utilizing its heat resistance, inflammation resistance, and mechanical properties. For example, the fiber of the present invention can be used as a woven fabric alone or in combination with other fiber groups, and can be used as a heat-resistant and anti-inflammatory fabric for fire-fighting clothes and protective clothing, an anti-inflammatory bedding, and a decoration material. In addition, it can also be effectively used as a non-woven fabric, various industrial materials such as filter membranes, or as a raw material for synthetic papers and composite materials, in particular, the processing and use of the meta-type wholly aromatic polyamide fibers of the present invention even at high temperatures. It maintains high strength and inhibits color or discoloration of the article. Therefore, it is particularly useful for applications for exposure to high temperature conditions, such as a base fabric for high temperature felts, a high temperature gas filtration membrane, or the like, or a matrix reinforcing material such as rubber or resin using its high modulus of elasticity. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples and the like. In addition, when "part" and "%" are not particularly limited, they are based on "quality", and when "quantity ratio" is not particularly limited, it means "mass ratio". Further, the polymer concentration (PN concentration) in the polymer solution (spinning dope) used for spinning is "mass % J of the polymer for "per mass parts", that is, [polymer / (polymer) +solvent + other)]X1 00 (%). <Measurement Method> Each of the properties of the examples and the comparative examples was measured by the following method. [Intrinsic Viscosity (IV)] The aromatic polyamine polymer was purified from the polymer solution, and dried, and then measured in a concentrated sulfuric acid of -24-201134993 at a polymer concentration of iOOmg/100 mL of sulfuric acid at 30 °C. [Monofilament fineness] The measurement according to the A method of the positive fineness was carried out in accordance with JIS L 1015, and the apparent fineness was expressed. [Broken strength, breaking elongation, and initial elastic modulus] The measurement was carried out under the following conditions using a tensile tester (manufactured by Instron Co., Ltd., model: 5565) in accordance with JIS L 1 0 15 . (Measurement conditions) Grab interval: 20 mm Initial load: 0.044 cN (1 / 20 g) / dtex Tensile speed: 20 mm / min [The amount of solvent remaining in the fiber (residual solvent amount)] The fiber was sampled at the outlet side of the washing step, The fiber was centrifuged at a centrifugal separator (rotation number of 5,000 rpm) for 1 minute, and the fiber mass (Ml) at this time was measured. The fiber was boiled in methanol of a mass of M2 g for 4 hours to extract a guanamine solvent and water in the fiber. The extracted fiber was dried in an environment of 1 〇 5 t for 2 hours, and the fiber mass (p ) after drying was measured. Further, the mass concentration (C) of the guanamine-based solvent contained in the extract was determined by a gas chromatography method. • 25- 201134993 The amount of solvent (melamine solvent mass) N (%) remaining in the fiber is calculated by the following formula using the above M1, M2, P, and C. N = [C/100]x[(Ml+M2-P)/P]xl〇〇 [300°C dry heat shrinkage] Hanging 98cN (100g) on a tow of about 3,300dtex, mutual Make a mark at 30 cm. After the load was removed, the tow was placed in an environment of 300 ° C for 15 minutes, and the length L between the marks was measured. The enthalpy obtained by substituting the measurement result L into the following formula is a dry heat shrinkage ratio (%) of 300 °C. 3〇〇°C dry heat shrinkage rate (%) = [(30-L)/30]xl00 [hue 値 (L * a b * )] For the obtained fiber, and in a dryer at 25 °C The fiber after heat treatment for 1 hour was subjected to measurement of hue. Specifically, a color color measuring device (manufactured by Macbeth Co., Ltd., trade name: Macbeth COLOR - EYE model CE - 3 1 00) was used, and measurement was performed under the following measurement conditions to determine the change in hue 値 (L* - b*). The number of hue 値(L * - b * ) is less than that of yellow. Further, L* and b* can be obtained by the three stimuli defined in JIS Z 8 7 2 8 (color diagram of the XYZ system of 1 〇 degree of view). (Measurement conditions) Field of view: 10 degrees -26- 201134993 Light source: D65 Wavelength: 360~740nm <Example 1> [Spinning stock solution (spinning stock solution) preparation step] The interfacial polymerization method was carried out by the method described in Japanese Patent Publication No. Sho 47-10863, and the intrinsic viscosity (IV) was 1.9. The phthalic acid m-phenylenediamine powder (20 parts) was suspended in 80.0 parts of N-methyl-2-pyrrolidone (NMP) cooled to -10 ° C to form a slurry. Then, the suspension was heated to 60 ° C to dissolve, and a transparent polymer solution was obtained. [Spinning step] The obtained polymer solution is used as a spinning dope to be spun from a spinning bath having a pore size of 〇.〇7 mm and a number of holes of 1,500, which is spun out at a bath temperature of 4 ° C. . The composition of the coagulating liquid was water/NMP (quantitative ratio) = 45 / 5 5 , and spinning was performed at a wire speed of 7 m / min in the coagulation bath. [Plastic extension step] Next, the film was stretched at a stretching ratio of 5.0 times in a plastic extension bath of a composition of water/NMP (amount ratio) = 40/60 at a temperature of 40 °C. [Washing step] After stretching, pass 2 (TC water / NMP (quantity ratio) = 70 / 30 bath (dilution length 1.8 m), then 2 (TC water bath (dip length 3 · 6 χ η), - 27- 201134993 Further warm water bath (immersion length 5 · 4m) at 60 ° C, followed by thorough washing in a warm water bath (immersion length 3.6 m) at 80 ° C. [Dry heat treatment step] Washed fiber, Then, a drying heat treatment is applied at a fixed length with a hot roll having a surface temperature of 15 ° C. [Heat Extension Step] Next, a heat treatment step is applied at a surface temperature of 33 (the heat treatment of the hot roll of TC is performed while applying a heat extension step of 1.3 times) Finally, poly(m-xylylenediphenyl) m-phenylenediamine fiber was obtained. [Measurement and evaluation] The obtained fiber (tow) was subjected to various measurement and evaluation. The fineness was 2.1 dtex, the breaking strength was 5.5 cN/dtex, and the breaking strength was broken. The degree is 24.0%, both of which are good numbers. In addition, the amount of residual solvent in the fiber is 0.4%, the dry heat shrinkage rate at 300 °C is 3.9%, the initial elastic modulus is 1,250 cN/mm2, and the heat shrinkage stability is excellent. The results obtained are shown in Table 1. <Example 2> In the preparation step of the spinning dope (spinning dope), a polymer solution was prepared by changing the solvent to be used to N,N-dimethylacetamide (DMAe), and this was used for spinning. A poly-m-xylylene meta-phenylenediamine fiber was produced in the same manner as in Example 1 except for the silk stock solution. Various measurements were made on the obtained fiber as shown in Table -28 - 201134993. <Comparative Example 1 > In the coagulation step, in the same manner as in Example 1, except that the composition of the coagulating liquid was changed to water/NMP (amount ratio) = 7 〇 / 30, the production of poly-m-xylylene benzene was carried out. Diamine fiber. The various measurement results of the obtained fiber are shown in Table 1. <Comparative Example 2 > A poly(m-xylylenediphenyl) m-phenylenediamine fiber was obtained in the same manner as in Example 1 except that the stretching ratio was changed to 1 · 〇 times in the heat stretching step. The various measurement results of the obtained fiber are shown in Table 1. <Example 3 > [Spinning stock solution (spinning stock solution) preparation step] In a reaction container under a dry nitrogen atmosphere, NMP 721.5 parts having a water content of 100 ppm or less were weighed to dissolve m-phenylenediamine 97.2 in the NMP. Parts (5 〇 · 1 8 mol%) 'Cool to 〇 °c. To the cooled n Μ P solution, 181.3 parts (4 9 · 8 2 mol%) of isophthalic acid chloride (hereinafter referred to as IPC) was further stirred and stirred to carry out a polymerization reaction. Further, after the viscosity change was stopped, stirring was continued for 4 minutes to complete the polymerization reaction. Then, 66.6 parts of calcium hydroxide powder having an average particle diameter of 10 μm or less was weighed and the polymer solution obtained by the polymerization reaction was slowly added to carry out a neutralization reaction. After the calcium hydroxide was put in, it was stirred for another 4 minutes to obtain a transparent polymer solution. -29- 201134993 After the purification of poly(m-xylylenediphenyl) m-phenylenediamine from the obtained polymer solution, the IV was determined to be 1 · 2 5 » In addition, the polymer concentration in the polymer solution was 2 〇 %. [Spinning step, plastic stretching step, multi-stage cleaning step, drying heat treatment step, heat stretching step] The obtained polymer solution is used as a spinning dope to make the spinning speed in the spinning step 5 m/min, and the plastic stretching step is plasticizable. A poly(m-xylylenediphenyl) m-phenylenediamine fiber was obtained in the same manner as in Example 1 except that the stretching ratio in the stretching bath was 6.5. The results of various measurements of the obtained fibers are shown in Table 1. <Example 4> In the preparation step of the spinning dope (spinning dope), the solvent used was changed to N,N-dimethylacetamide (DM Ac ), and the same procedure as in Example 3 was carried out. In the polymer solution, the obtained polymer solution was used as a spinning dope, and in the same manner as in Example 1, a poly(m-xylylenediphenyl) m-phenylenediamine fiber was obtained. The results of various measurements of the obtained fibers are shown in Table 1. <Comparative Example 3 > In the solidification step, the composition of the 'coagulating liquid was changed to water/NMP (quantity ratio) = 3 0 / 70'. In the same manner as in Example 3, poly(m-xylylenediphenyl) m-phenylenediamine was obtained. fiber. The various measurements of the obtained fibers are shown in Table 1 ^ <Comparative Examples 4 to 5 > In the heat extension step, the stretching ratio was changed to 1. In addition to the 〇 times, each of the benzenediamine fibers of Example -30 and Example 4 was obtained in the same manner as in Example -30-201134993. Hyperthyroidism. The results of various measurements of the obtained fibers are shown in Table 1. -31 - 201134993 [i] Comparative Example 5 DMAc 45/55 vn vd 330 p <N CN ON (N 20.5 fO d 00 (N Ο VD 77.8 73.7 Comparative Example 4 NMP 45/55 in vd 330 q iS <n 18.0 d <N 710 78.3 1 75.8 Comparative Example 3 NMP 30/70 vd os CNi 35.0 <N Ό o v〇 71.1 66.2 Comparative Example 2 NMP 45/55 o ... 330 Ο CN (N 卜 rn 28.5 On 〇 heart CO o 卜 78.5 76.3 丨Comparative example 1 NMP 70/30 o 330 ΓΛ 〇 ΓΟ 14.0 <N oo 72.1 67.6 j Example 4 DMAc 45/55 vd 330 fO (N r^i 00 wS 18.9 0.08 v〇rn 1 1180 78.9 77.7 Example 3 NMP 45/55 VO rn port o 18,5 d On 1170 79.0 j 78.5 Example 2 DMAc 45/55 O vri 330 (N r oo CN 990 79.5 77.8 Example 1 NMP 1 i 45/55 o 330 ro wS 24.0 inch ό ON rn 1250 1 79.7 ! 77.1 Polymer Dissolved Ammonium Solvent Coagulation Bath Hydrazine Solvent Composition (Water/Solvent) § s Ρ m (dtex) (cN/dtex) g Vw/ /—V (cN/mm2) Hue before heat treatment (L * -b *) Hue after heat treatment at 250 °C (L*-b*) Plastic extension ratio Thermal elongation temperature Thermal extension ratio Denier rupture strength Breaking elongation Residual solvent amount 300 °C Dry heat shrinkage rate Initial modulus of elasticity -32- 201134993 [Industry According to the present invention, it is possible to provide a solvent which is extremely small in mechanical properties, heat resistance and the like and substantially free of layered clay mineral wholly aromatic polyamide fibers (especially, poly(m-xylylenedifluorene)) Therefore, the use of the meta-type wholly aromatic polyfiber product of the present invention inhibits coloration even under processing and use conditions at high temperatures. Discoloration. Therefore, the meta-type peramine fibers of the present invention are useful especially in the field of processing or use at high temperatures. Good and maintainable strength of the interstitial phenylenediamine fibrin fiber of the fiber-like aromatic polyfluorene-33 -