200426161 (1) 玖、發明說明 【發明所屬之技術領域】 本發明，係關於均壓性，通氣性，粉塵捕集性優異之 聚四氟乙燒抄製紙，爲其原料之聚四氟乙烯纖維狀粉體， 前述抄製紙所成成形物’及生産效率優異之聚四氟乙烯纖 維狀粉體之製造方法。詳言之，係關於製紙時可得到表面 平滑’通氣性優異之聚四氟乙烯製紙之聚四氟乙烯纖維纖 維狀粉體之製造方法。 Φ 【先前技術】 聚四氟乙烯（以下，簡稱爲PTFE )係具有優異耐藥 品性，耐熱性，機械特性，電特性者，其用途以工業用途 爲中心而呈現多樣化。因此，其使用形態亦爲多樣化，紙 狀品亦可使用於紙狀品濾紙，斷熱材（a d i a b a t 〇 r )，絕緣 材料等。 紙狀品之製造方法方面，各種方法爲周知。例如，日 Φ 本特公昭45-8165號公報，揭示平均纖維長1〇〇〜5〇〇0//m ，平均形態係數5以上之PTFE纖維狀粉末或者對此使充 塡材均勻混合所成之組成物在液體中分散成爲紙料，將此 予以製紙，乾燥後，自基材將製紙剝離予以煅燒之方法。 在此所使用之PTFE纖維狀粉末，係將原料PTFE在高温 中以強剪切力作用，使之粉碎所得者。並在粉碎時，將粉 碎機本身加熱，或者將粉末加熱亦可者被記載，進而亦記 載將熱風吹入同時予以粉碎之方法爲最佳。 -5- 200426161 例知 施習 實 。 及載 容記 内無 施亦 實件 地條 體度 具溫 就之 ， 時 此理 於處 止碎 僅粉 載於 記 關 其而 2)是示 彳但揭 無 並 ，係在20〜5(TC左右之溫度條件進行粉碎處理，但在此溫 度條件處理時，會產生粒徑5 # m以下之比較細的PTFE 粉末，會造成通氣性低，硬的PTFE製紙之問題。 相對於此本發明人等，則如日本特公昭40- 1 1 642號 公報，或者日本特公昭45- 1 4 1 27號公報等所記載，發現 了 PTFE抄製紙之製法，並發現其襯墊性，均壓性優異。 但是，關於可具有滿足何種性質之PTFE纖維狀粉體的話 ，會得到適於襯墊材，濾材等均勻的抄製紙則尙無定論。 又爲了改善機械強度則手工之補強絲之裝設或金網（ wire netting)所致之襯裡（lining)爲必要，結果會有歪 斜（distortion )之不均勻性使耐用壽命變短等問題，除 此以外，爲活用PTFE之優異電特性以用作基板材之情形 ，由於自我保持性之問題使得薄化爲困難。 【發明內容】 本發明，係使前述課題明朗化，而對此予以克服者， 其係提供一種具有均勻的物性分布，凝集性，均壓性，通 氣性，粉塵（dust)捕集性優異之PTFE抄製紙，爲其原 料之PTFE纖維狀粉體，前述PTFE抄製紙所成成形物， 及生産效率優異之前述PTFE纖維狀粉體之製造方法。 亦即，本發明係關於，在以每分5 °C之升溫速度進行 之差式掃瞄型熱量計分析中，所得之熔融吸熱曲線中低溫 -6 - (3) (3)200426161 處之峰値面積比率爲全峰値面積之88.5%以上之PTFE纖 維狀粉體。 前述PTFE纖維狀粉體中，平均纖維長100〜5000 /zm ，及平均形態係數5以上爲佳。 藉由氮吸附法所測定之比表面積爲4.0 m 2 / g以上爲佳 〇 又，本發明，係關於以前述PTFE纖維狀粉體爲原料 ，經過製紙步驟所得之聚四氟乙烯抄製紙。 再者本發明係關於，每分5 °C之升溫速度所進行差式 掃瞄型熱量計分析中，所得熔融吸熱曲線中低溫處之峰値 面積比率爲全峰値面積之88.5%以上，平均纖維長爲100〜 5 00 0 β m，平均形態係數爲5以上之聚四氟乙烯纖維狀粉 體之製造方法，將原料聚四氟乙烯粉末藉由供給裝置引入 加料漏斗之步驟，將前述原料聚四氟乙烯粉末自前述加料 漏斗供給於拉伸處理槽之步驟，藉由拉伸手段予以拉伸處 理之步驟，及拉伸處理後予以分級之步驟所成，聚四氟乙 烯纖維狀粉體之製造方法。 在前述製造方法中，自加料漏斗至拉伸處理槽之原料 聚四氟乙烯粉末之供給，以使用介質之流動來進行爲佳。 藉由拉伸處理後所進行之分級步驟，以可除去粒徑 5.Ο/zm以下之聚四氟乙烯粉末爲佳。 在前述拉伸處理時由前述拉伸手段添加於聚四氟乙烯 粉末之能量以10〜200kcal/kg爲佳。 又，本發明，係關於由前述PTFE抄製紙所得之成形 (5) (5)200426161 合•成長反應並不相同，很多來自周圍剪切力等之外力或 ，在受到分子間力之干渉中，亦有組織化之分子。 在使PTFE粉體成形煅燒之過程，分子之解折疊更加 進行，組織間之熔融黏著多所產生，不僅可獲得凝集力優 異之不至於崩形之成形品，在抄製紙之情形應力亦可被均 勻地傳達，成爲均壓性優異之物。 分子鏈之解折疊在升溫中是否會發生已如前述，而在 僅依存於熱性解折疊操作之情形，其均勻的控制有困難， 而遭受部分爲過剩熱之情形其部位會強固地被組織化，而 造成與其他組織之熔融黏著性喪失之問題。爲了迴避此問 題經外力之解折疊時，以與熱所致解折疊倂用爲佳。 在分子之解折疊完成之情形場合，抄製紙之成形無法 在恰當狀態進行之情況相當多。吾人認爲此係在抄紙之操 作過程中，施予PTFE纖維狀粉體之外力及熱，可進行其 組織化，而作爲抄製紙予以組織化之際之最適狀態予以通 過爲其原因。因此PTFE纖維狀粉體在製紙前爲最適之解 折疊狀態，在控制抄製紙之性狀上爲必要者，此爲易於理 解者，解折疊完全完成後之PTFE物體之DSC曲線上之融 化峰値單一峰値，會偏移至3 25〜3 28 °C附近，在本發明之 PTFE纖維狀粉體並無含有。 差式掃瞄型熱量計中所得之熔融吸熱曲線中峰値面積 ，與其熱量成正比例，又在一般容許之範圍中可謂與其分 子之數成比例者。因此，如第1圖所示，具有二個峰値或 者肩部之明確的一個峰値之DSC曲線如虛線所示，在二 (6) (6)200426161 個正規分布或者分離於其他分布曲線之情況，吾人可認爲 低溫處之峰値（PL)之面積與被解折疊之分子之數成比例 者，而高溫處之峰値（PH)之面積與不被解折疊之分子 之數成比例者，故被解折疊之PTFE分子之比率，在差式 掃瞄型熱量計中所得之熔融吸熱曲線中低溫處峰値（Pl ) 之面積與全峰値面積之比來予以評價爲可行。 具有雙重峰値或者明確的肩部之單一峰値，在數學上 可以因3個以上複數之正規分布所致合成曲線來理解，吾 φ 人認爲因具有二個頂點故以二個正規分布或者類似於此之 分布曲線來分離者爲充分且妥當，在本發明之檢討中亦可 得妥當之結果。此係部分被解折疊之分子，在評價上解折 疊爲必要之熱量爲小之方式，使含於無法被解折疊之分子 之正規分布者，來理解即可。 前述複合吸收峰値，通常係使用 Gaussian-Lorentian 型之曲線之近似而予以分離爲可行。與僅使用 Gaussian 型或者僅使用Lorentian型之曲線之任一種之情況比較以 φ 乖離程度較少爲其特徵者，在市售之多種分析機器中附屬 之計算軟體亦有使用此種方法。本發明中爲原料之PTFE 粉體所見外觀上之二個頂點被賦與初期値，對此不予限制 而作爲近似，可決定基本的峰値位置。藉此所得基本峰値 位置爲3 3 9.1 4°C與3 43.0 1 °C，以此爲基準則線形·半寬 度（full width at half maximum)並無限制，自僅爲峰値 温度之初期値限定爲0.6〜0· 7 °C以下予以近似，將複合曲 線分離成爲二，來求得其峰値面積。在此次之檢討中爲使 -10- (7) (7)200426161 値之收斂（c ο n v e r g e n c e )所需時間予之縮短，係利用原 料粉體之情報，但亦可直接自纖維狀粉體之融化曲線求得 〇 本發明之PTFE纖維狀粉體，每分之升溫速度進 行差式掃瞄型熱量計分析，所求得熔融吸熱曲線之低溫處 之峰値面積，爲全峰値面積之8 8.5%以上，而以92.0%以 上，99.5%以下爲佳。低溫處峰値面積不足全峰値面積之 88.5%之情形，凝集力不足會有成形品之崩形易於產生之 傾向，又，所得抄製紙之襯墊性亦有缺乏之傾向。低溫處 之峰値面積過大，亦即無法見到二個峰値（或者肩部）之 情形，抄製紙之成形無法成爲較佳狀態之情形爲多時，則 已如上述。 一般在製紙或壓縮成形等之成形方法，與分子等級之 伴隨均勻的融化之成形方法不同，原料之比表面積與其凝 集力，亦即成形物之機械特性大爲相關，在某一定之範圍 中比表面積越大，則可提高其成形物之機械特性。此係各 個原料之接觸面積增大，則使作爲組織之應力傳達點增加 ，結果則組織全體之機械特性會因而提高。此與PTFE之 情況亦相同，PTFE纖維狀粉體之比表面積越大，則其凝 集力增大，作爲組織不會崩形而可獲得機械特性優異之物 。一方面PTFE纖維狀粉體彼此之間之熔融黏著產生越多 ，則抄製紙之比表面積變小，則可顯示某一定程度以上之 比表面積之減少率，亦爲推測抄製紙物性上重要的參數。 此在，PTFE纖維狀粉末及其成形品之場合亦爲相同 (8) (8)200426161 ，PTFE纖維狀粉末之比表面積越大，則其凝集力變大， 可得到不會崩形，機械特性優異之成形品。因此，在本發 明中，PTFE纖維狀粉末之比表面積以4.0m2/g以上爲佳 ，5.0 m2/g以上，8.5 M 2/g以下更佳。另外，在此所謂比表 面積，係藉由氮吸附法所測定之値。比表面積不足 4〇m2/g之情形，凝集力不足在成形時崩形易於產生。又 ，成形品缺乏均勻性，無法得到所望之物性。比表面積比 8.5m2/g更大之情形，纖維狀粉體易於被緻密充塡所得之 · 抄製紙之目付重量（1目付=4.3 05 5 g/ m2 )變大，通氣 性降低，有無法顯現襯墊性之傾向。 又，爲了發揮紙之特性原料粉體之形狀以纖維狀爲佳 ，一般而言可以形態係數表示纖維狀，但關於採用多數之 長鬍子般的形狀之不定形粉體，則在顯示紙之凝集力之一 方，在形態係數方面也有無法以纖維狀表示之情形。在此 情形將比表面積與形態係數合倂予以規定，可予以判斷是 否作爲紙之性質得以發揮之原料。有鑑於此，則所謂纖維 # 狀，係其全部乃至一部份被外力所拉伸，在物性方面顯示 向異性所得者來考慮較佳。 本發明中所使用原料PTFE方面，以四氟化乙烯（以 下，簡稱TFE)之單獨聚合物亦可，TFE9 5〜1 0 0莫耳 %與，選自式（I): CX2= CY ( CF2 ) nZ ( I ) (式中，x，Y及z爲相同或相異，可爲任意氫原子 或氟原子，η爲1〜5之整數）所示氟烯烴，及式（II): -12- (10) (10)200426161 首先將前述原料PTFE粉末自供給機投入原料加料漏 斗，進行自原料加料漏斗對拉伸處理槽之原料PTFE粉末 之供給。對拉伸處理槽之原料PTFE粉末之供給，因自重 而落下亦可，因原料PTFE粉末之形態可機械式的進行， 而爲完全控制所得之PTFE纖維狀粉體之形狀，則以由液 體或氣體等流動性高的介質來進行較佳。在拉伸處理槽 ，設有拉伸手段（詳細如後述），將原料PTFE粉末予以 拉伸處理成爲 PTFE纖維狀粉體。在此，在處理原料 PTFE粉末之際，於步驟中添加於PTFE粉末之能量被控 制，而以控制PTFE纖維狀粉體之解折疊之進行度爲佳。 接著，藉由分級裝置，僅選別可充分拉伸之粉末，並 送至後續之分級裝置。其他以外之粉末則回至拉伸處理槽 ，予以進一步處理。最後，藉由分級裝置（測定方法如後 述），將粒徑5 // m以下之PTFE粉末除去，得到本發明 之PTFE纖維狀粉末。 以下，就各步驟予以詳述。 在將前述原料PTFE粉末自原料加料漏斗供給於拉伸 處理槽之步驟中，在使用粒徑小之情形，則在加料漏斗内 固化，而以自重落下供給有其困難。此情形則以水等之液 體爲介質可對拉伸處理槽強制地供給。所得PTFE纖維狀 粉體並不即時供至製紙步驟而貯藏之情況，因使用液狀介 質並不合適，故將乾燥空氣等之氣體作爲介質進行原料 PTFE粉體之供給。但是，拉伸處理槽内之旋轉體動作， 或者拉伸處理完畢之原料PTFE粉體之排出會受到影響故 -14- (11) (11)200426161 並不合適。藉由此等操作，可非常有效的製造平均纖維長 100〜5000/zm，平均形態係數5以上之PTFE纖維狀粉末 又拉伸處理温度，以可利用拉伸時之摩擦熱爲佳。藉 此，變成易於原纖化，可傾向於得到比較穩定之纖維長之 粉末。因此，在前述拉伸手段方面，以利用摩擦力來進行 拉伸處理較佳。此種拉伸手段方面，有例如錘磨（ hammer mill )，篩磨等，藉由旋轉體僅在一方向施予剪 切力，將原料粉體予以拉伸所得裝置爲佳。 在前述拉伸處理時自拉伸手段添加於PTFE粉末之能 量被控制於10〜200kcal/kg，可防止PTFE塊狀物之發生 。尤其是，能量以控制於10〜60kcal/kg爲佳。藉此所得 PTFE纖維狀粉末所製紙之PTFE紙，纖維狀粉體彼此之 間之交纏多而可得，局部則伴隨粉彼此間之熱熔融黏著可 得到襯墊性優異之PTFE抄製紙。在此，自拉伸手段添加 於PTFE粉末之能量不足lOkcal/kg時，短纖維狀粉末變 多而無法獲得充分之物理的交纏。又，前述能量超過200 kcal/kg時，纖維狀粉體彼此之間之熱熔融黏著會難以產 生。 在此，拉伸處理時自拉伸手段添加於PTFE粉末之前 述能量，係以供與拉伸手段之能量予以定義。供與拉伸手 段之能量，係將PTFE粉末以前述拉伸手段拉伸之際，爲 維持拉伸旋轉數所需要之前述PTFE粉末每lkg之能量， 在拉伸時與空轉時可自拉伸手段之電流値之差求得。使用 -15- (12) (12)200426161 介質對拉伸處理槽供給原料之情形，所供與之熱量係以 4 0°C以下之室温爲基準，必須由與介質之温度差所賦與之 熱量來算出。 在進行PTFE粉末處理之後予以分級之步驟中，於原 料PTFE粉體處理後，藉由分級裝置進行分級操作。進行 此分級操作，使得拉伸不充分之PTFE纖維狀粉末，可防 止自拉伸處理槽流出。因此，具有平均纖維長100〜5 000 //m之PTFE纖維狀粉末可有效率的獲得。尤其是，平均 __ 纖維長以10 0〜4 000/zm爲佳。前述平均纖維長不足100 /zm時，在製紙之際，自網狀之基材一部份脫落，而爲針 孔之原因。又，平均纖維長超過5 000 // m時，因纖維長 度長，故要製造厚度均勻的紙有困難。分級裝置方面，可 舉出分級用篩（screen )等，以所定尺寸爲境界將粉體分 離所得之物爲佳。 進而，將粒徑5 // m以下之PTFE纖維狀粉末予以除 去，可提高使用前述粉末製紙之PTFE抄製紙之通氣性， φ 就柔和地襯墊性優異之點爲佳。進而，將粒徑1 〇 m以 下之PTFE纖維狀粉末予以除去爲佳。 在此，前述粒徑之測定，係使用雷射繞射式粒度分布 測定裝置HELOS&RODOS系統（SYMPATEC公司製）， PTFE纖維狀粉末係以3bar之壓縮空氣予以分散同時測定 之。粒徑係指50%粒徑。 又，PTFE纖維狀粉末之平均形態係數以5以上爲佳 ，1 〇以上更佳。又，平均形態係數之上限値並無特別限 -16- (13) (13)200426161 定’以1 〇〇〇以下爲佳。前述平均形態係數係指，以纖維 寬度除以纖維長所得之物。前述平均形態係數比5更小時 ，在煅燒後難以自網狀之基材剝離，表面平滑性或外觀（ 起毛，歪斜）等差，會成爲完工後不良之紙。如此所得 PTFE纖維狀粉末，係由以下之方法，來製紙。首先，前 述PTFE纖維狀粉末，係藉由分散劑被均勻地分散於水中 ，成爲紙料。此時紙料上，可添加有機高分子強化纖維， 無機充塡材等。將此紙料在網狀等之基材上製紙。其後， 予以乾燥，煅燒，可得到PTFE製紙。尤其是含有有機高 分子強化纖維之情形，可在更大面積之濾器不予襯裡下設 置，藉此可謀求濾器單元之小型化。 製紙所得PTFE製紙之厚度，有依其用途而定，以 0.02mm以上，8.00mm以下爲佳，在 0.05mm以上， 6.00mm以下更佳，在O.lOmm以上，4.00mm以下特佳。 厚度不足〇.〇2mm之情形，在作爲濾器使用之情形，會有 捕集能力不足之傾向。厚度比8.00mm更大之情形，抄製 紙因自重造成紙夾（clip )變形，會有損及目付（pile w e i g h t )之均勻性之傾向。 又’製紙所得PTFE製紙之表面平滑性以10.5 μ m以 下爲佳，以10.0// m以下更佳。表面平滑度比10.5// m更 大之情形，在處理（handling )時起毛（scuffing )，會 有產生粉塵（dust )之傾向。另外，在此所謂表面平滑性 ，係如後述，以觸針式表面粗度計來計算算術平均粗度。 又，製紙所得PTFE製紙之透氣度，依PTFE製紙之 (15) (15)200426161 於此等真知灼見亦可得到混合抄製紙。如此，複合化之對 應材料爲了不損及PTFE之高耐熱性，其融點以200 °C以 上爲佳，更佳爲220°C以上。其成分並非必要爲有機物， 可因應目的選擇適宜的1種或2種以上之對應材料。該等 之例方面，可舉出聚對伸苯基苯並啤唑，液晶性聚酯，芳 族聚醯胺紙漿，玻璃，碳等之各纖維，但本發明並非限定 於該等之例。又融點係藉由DSC法來求得之數値。 如前述爲維持耐熱性，則以複合化之際之對應材料以 具有高耐熱性者爲佳，在耐熱性並非特別必要之用途方面 並非有具備高耐熱性之必要。例如爲持續維持PTFE所具 備之帯電特性，在要提高其抄製紙強度之情形可選擇丙烯 酸纖維之裁斷物，類纖維等作爲對應材料，依照lofting 加工等使得體積增大之抄製紙予以膨張，則可選擇聚醯胺 ，聚酯，聚烯烴等爲對應材料。 本發明之抄製紙，因其優異耐熱性可是用於各種用途 ，而依情況之不同使得前述複合抄製紙化，進而可使用適 合之物。例如作爲壓縮成形用中心材使用時，可防止薄片 沖壓（sheet stamping)成形物與模具之邊緣部之擦傷之 發生，可連續確保優異之離型性。又作爲濾材使用時，除 了可静電方式集麈以外，亦可發揮對強酸，強鹼之耐久性 ，高温下之濾別性。作爲電線捲繞被覆材使用時，因在内 部具有空孔故可發揮更優異之絶緣特性之外，亦可期待作 爲絕熱層之特性。在成爲筒型帶材時可使用筒狀之無縫（ seamless)篩孔來製紙，可容易獲得無縫，離型性優異之 -19- (16) (16)200426161 無縫帶，進而，若強度爲必要則可與強化纖維混合來製紙 。用作焊錫反流加工用定位型紙時，焊錫附著亦少’可期 待作業性更加提高。作爲絶緣紙使用之情形’可防止自周 圍之液劑等之附著，可安全地，長時間保護幫浦單元等之 控制部。在伴隨資訊處理速度，通信速度之高速化之電路 基板材，可求得對應於高周波之低誘電率，對此在適用於 PTFE製紙或者混合抄製紙時，不僅可發揮優異電特性， 若與強化材複合化時，亦可期待充分之尺寸安定性，耐熱 φ 性。如日本特開2002-23 1 3 1號公報所示，使PTFE製紙在 液晶製造生產線中係作爲襯墊材使用爲周知，在其他之用 途中所求得之襯墊性爲各種各樣，在要求尺寸安定性或耐 磨耗性之範圍可適用混合抄製紙。 因PTFE纖維狀粉體爲非常體積大之狀態，在乾燥狀 態與其他材料之混合亦爲非常容易，故作爲複合成形物之 原料爲恰當。 在該等之用途中，與其他材料複合化之情形，若 Φ PTFE之重量分率不足2%時PTFE之特性無法充分發揮， 又超過98 %時，添加PTFE以外成分之効果則無法充分獲 得。因此混合成形物所含有PTFE以外成分之重量分率以 2〜98%爲佳，更佳爲4〜96%，特佳爲5〜95%。 接著’根據本發明之實施例進而予以具體説明，但本 發明並非僅限於此。 另外’本發明之實施例所測定之各物性値，係由下列 之方法所測定者。 -20- (17) (17)200426161 (平均纖維長） 粉末以電子顯微鏡測定，以算術平均求得纖維方向之 長度200點以上，在測定時，並不測定長度80 // m以下 之物。 (平均形態係數） 粉末係以電子顯微鏡測定，將所得纖維方向之長度以 φ 纖維寬度除之，所得形態係數200點以上爲藉由算術平均 來求得之値，在測定之時，則並不測定長度80 // m以下 之物。 (透氣度） 將PTFE製紙，使用galare試驗機，測定3 00mL之空 氣通過1 cm 0之銳孔所需要之時間。 (表面平滑性） 藉由PTFE製紙以觸針式表面粗度計，來測定算術平 均粗度。 (襯墊性） 使用壓縮試驗機（compression tester)，測定PTFE 製紙之壓縮工作量及1 〇次來回情況之壓縮回復工作量， 將標準樣本以爲1 00時之相對値表示。襯墊性越大則數値 -21 - (18) (18)200426161 越大。標準樣本係指，壓縮回復工作量/壓縮工作量x i 〇〇 (% )之値爲60%之PTFE製紙。 (差式掃瞄型熱量測定） 使用Seiko instruments公司製RPC-220，在升溫速度 5°C /分，樣本量3mg進行測定。以JIS-K7123爲參考。 (峰値面積比率） # 以每分5 °C之升溫速度進行差式掃瞄型熱量計分析， 將所得DSC曲線使用Gauss ia n-Lore nti an型之曲線，分離 成爲二個峰値曲線，將低溫處峰値之面積以全峰値面積除 算，來算出峰値面積比率。 (製紙厚度） 該PTFE製紙係使用測微表（dial gauge ) Η型（加壓 200g以下之型式）加以測定。 φ (比表面積） 使用湯淺Ionics公司製Biosorb，於標準附帶電池， 藉由氮吸附法，進行粉體之比表面積之評價。 (拉伸強度） 使用 Orientic公司製萬能試驗機（Tensilon) STA-1150，15mm寬之樣本以夾盤（chuck)間距離 100mm， -22 - (20) (20)200426161 ，可獲得表面平滑之物。又任〜之紙在裁斷時於端部並不 〆 會產生開線，可發揮良好之凝集力。 表1 實施例 1 實施例 2 實施例 3 製造條件 能量（kcal/kg) 3 7 52 70 纖維狀 粉末 平均纖維長（m m) 0.4 1 .5 2.5 平均形態係數 11 40 68 峰値面積比率（％) 90.9 92.3 93.1 比表面積（m2/g) 5.83 6.38 6.69 PTFE製紙 製紙厚度(mm) 0.49 0.52 0.5 1 表面平滑性（// m) 7 5 7 透氣度 (sec/cm 0 · 3 00mL) 9.5 7.0 6.5 襯墊性 92 105 1 10 拉伸強度（MPa) 1.2 1.5 1.6 比較例1〜3 以表2記載温度之熱風將原料p T F e粉末供給於拉伸 處理槽，除了予以拉伸處理以外，得到與實施例1同樣 PTFE纖維狀粉末。所得PTFE纖維狀粉末，各自具有表2 所記載之平均纖維長，平均形態係數，峰値面積比率及比 表面積。 -24- (21) 200426161 接著，與實施例1同樣製紙，得到各自厚度 0.47〜〇.51mm之PTFE製紙。所得PTFE製紙之表面平滑 性，透氣度，襯墊性，及拉伸強度，係如表2所示。在比 較例1所得PTFE製紙透氣性顯著變差，完全不適於濾器 用途。又在任一之PTFE製紙中與裁斷時會產生開線，可 確認切斷部分之尺寸保特性差。 表2 _ φ 比較例 1 比較例 2 比較例 3 製造條件 能量爲（kcal/kg) 8 102 95 熱風温度（°C ) 55 82 80 纖維狀 粉末 平均纖維長（mm) 0.2 5.5 5.2 平均形態係數 4 17 1 145 峰値面積比率（％) 85.0 嶔1 ※1 比表面積（m2/g) 3.0 7.1 7.0 PTFE製紙 製紙厚度（m m) 0.47 0.50 0.5 1 表面平滑性（// m) 11 2 1 23 透氣度 (sec/cm 0 · 3 OOmL) 14.5 4.5 5.5 襯墊性 75 84 89 拉伸強度（MPa) 0.5 ※2 0.9200426161 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a polytetrafluoroethylene fired paper which is excellent in pressure equalization, air permeability, and dust trapping property, and a polytetrafluoroethylene fiber as a raw material. Powder, a method for producing a polytetrafluoroethylene fibrous powder having excellent production efficiency and a molded article formed from the aforementioned paper. Specifically, the present invention relates to a method for producing a polytetrafluoroethylene fiber fibrous powder capable of obtaining a polytetrafluoroethylene paper having a smooth surface and excellent air permeability during paper making. Φ [Prior technology] Polytetrafluoroethylene (hereinafter referred to as PTFE) has excellent chemical resistance, heat resistance, mechanical properties, and electrical properties, and its uses are mainly diversified in industrial applications. Therefore, its use forms are also diversified, and paper-like products can also be used for paper-like filter paper, thermal insulation materials (a d i a b a t 〇 r), insulation materials, and the like. As for the manufacturing method of a paper-like product, various methods are well-known. For example, Japanese Patent Publication No. 45-8165 discloses a PTFE fibrous powder having an average fiber length of 100 to 50000 // m and an average morphology coefficient of 5 or more. The composition is dispersed in a liquid to form a paper material, which is then made into paper. After drying, the paper is peeled from the substrate and calcined. The PTFE fibrous powder used here is obtained by crushing the raw material PTFE at a high temperature with a strong shearing force. During the pulverization, it is recorded that the pulverizer itself is heated, or the powder is heated, and it is also described that the method of blowing hot air and pulverizing the powder at the same time is the best. -5- 200426161 Case study practice. And there is no application in Yi Rong Ji, but the physical condition is warm. At this time, the principle is only broken. Only the powder is contained in Ji Guan Qi. 2) It is shown but unexplained, it is about 20 ~ 5 (TC The pulverization treatment is performed under the temperature condition, but a relatively fine PTFE powder with a particle size of 5 # m or less is generated under the temperature condition, and the problem of low air permeability and hard PTFE paper is caused. As described in Japanese Patent Publication No. 40-1 1 642 or Japanese Patent Publication No. 45-1 14 1 27, etc., a method for producing a PTFE paper is found, and it is found that it has excellent cushioning properties and equalizing properties. However, it is inconclusive as to what kind of PTFE fibrous powder can be used, which can be used to produce uniform paper, such as gaskets, filters, etc. In order to improve the mechanical strength, the installation of manual reinforcing wires or The lining caused by wire netting is necessary, and as a result, the unevenness of distortion will shorten the durability and other issues. In addition, it uses the excellent electrical characteristics of PTFE to be used as a base material. Situation due to self The problem of retentivity makes thinning difficult. [Summary of the Invention] The present invention is to make the aforementioned problem clear, and to overcome it, it provides a uniform physical property distribution, agglutination, pressure equalization, and air permeability. , PTFE fibrous paper with excellent dust trapping properties, PTFE fibrous powder as its raw material, the formed product of the aforementioned PTFE fibrous paper, and the manufacturing method of the aforementioned PTFE fibrous powder with excellent production efficiency. The present invention relates to the peak-to-peak area of the low-temperature -6-(3) (3) 200426161 of the melting endothermic curve obtained in a differential scanning calorimeter analysis performed at a heating rate of 5 ° C per minute. A PTFE fibrous powder having a ratio of 88.5% or more of the total peak area. The aforementioned PTFE fibrous powder preferably has an average fiber length of 100 to 5000 / zm and an average morphology coefficient of 5 or more. It is determined by a nitrogen adsorption method The specific surface area is preferably 4.0 m 2 / g or more. The present invention relates to a polytetrafluoroethylene paper-making paper obtained by using the aforementioned PTFE fibrous powder as a raw material through a paper-making step. Furthermore, the present invention relates to each At 5 ° C In the analysis of the differential scanning calorimeter at the temperature and speed, the peak-to-peak area ratio at the low and middle temperature of the obtained melt endothermic curve is more than 88.5% of the total peak-to-peak area, and the average fiber length is 100 to 5 0 0 β m. A method for manufacturing a polytetrafluoroethylene fibrous powder having a coefficient of 5 or more, a step of introducing a raw polytetrafluoroethylene powder into a feeding funnel through a feeding device, and supplying the aforementioned raw polytetrafluoroethylene powder from the feeding funnel to a stretching The step of processing the tank, the step of performing a stretching treatment by a stretching means, and the step of classifying after the stretching treatment, a method for manufacturing a polytetrafluoroethylene fibrous powder. In the aforementioned manufacturing method, the supply of the raw material polytetrafluoroethylene powder from the charging funnel to the stretching treatment tank is preferably performed by using the flow of the medium. Through the classification step performed after the stretching treatment, it is preferable to remove polytetrafluoroethylene powder having a particle size of not more than 5.0 / zm. The energy added to the polytetrafluoroethylene powder by the stretching means during the stretching treatment is preferably 10 to 200 kcal / kg. In addition, the present invention relates to the forming (5) (5) 200426161 obtained from the aforementioned PTFE paper making. The growth and growth reactions are not the same. Many of them come from external forces such as surrounding shear forces, or they are dried up by intermolecular forces. There are also organized molecules. In the process of forming and calcining the PTFE powder, the unfolding of the molecules progresses more, and more fusion and adhesion between the tissues is generated. Not only can the molded product with excellent cohesion not be collapsed, but also the stress in the case of paper making It is uniformly conveyed, and it is excellent in pressure uniformity. Whether the unfolding of the molecular chain will occur during heating as described above, but in the case of relying only on the thermal unfolding operation, it is difficult to control uniformly, and the part that is subjected to excessive heat will be strongly organized , And cause the problem of loss of melt adhesion with other tissues. In order to avoid this problem, it is better to use unfolding with heat when unfolding by external force. In the case where the unfolding of the molecule is completed, there are many cases where the forming of the copied paper cannot be performed in an appropriate state. In my opinion, this is the organization of the PTFE fibrous powder during the papermaking operation, and it can be organized as the optimum state when the papermaking is organized. Therefore, the PTFE fibrous powder is in an optimal unfolded state before papermaking, and it is necessary to control the properties of the papermaking. This is easy to understand. The melting peak on the DSC curve of the PTFE object after unfolding is complete is single. The peak peak shifts to around 3 25 ~ 3 28 ° C, and is not contained in the PTFE fibrous powder of the present invention. The area of the peaks in the melting endothermic curve obtained in the differential scanning calorimeter is directly proportional to its heat, and it can be said to be proportional to the number of its molecules in the generally allowable range. Therefore, as shown in Figure 1, the DSC curve with two peaks or a clear peak at the shoulder is shown as a dashed line, between two (6) (6) 200426161 regular distributions or separated from other distribution curves In some cases, we can consider that the area of the peak ridge (PL) at low temperature is proportional to the number of unfolded molecules, and the area of the peak ridge (PH) at high temperature is proportional to the number of molecules that are not unfolded. Therefore, the ratio of the unfolded PTFE molecules in the melting endothermic curve obtained in the differential scanning calorimeter to the ratio of the area of the peak 値 (Pl) at the low temperature to the area of the full peak 値 is evaluated as feasible. Single peaks with double peaks or explicit shoulders can be mathematically understood by the composite curve caused by the normal distribution of more than three complex numbers. We believe that two regular distributions are used because they have two vertices or It is sufficient and appropriate to separate the distribution curve similar to this, and proper results can also be obtained in the review of the present invention. This is a partially unfolded molecule. In the evaluation, unfolding is necessary to reduce the amount of heat necessary for the regular distribution of molecules that cannot be unfolded to understand. The aforementioned composite absorption peaks 通常 are usually separated as feasible using an approximation of a Gaussian-Lorentian curve. Compared with the case where only Gaussian type or only Lorentian type curve is used, it is characterized by a small degree of deviation from φ. This method is also used in the calculation software attached to a variety of commercially available analysis machines. The two peaks in the appearance of the PTFE powder used as the raw material in the present invention are assigned to the initial ridge. This is not a limitation and the approximate peak ridge position can be determined as an approximation. The basic peak position obtained from this is 3 3 9.1 4 ° C and 3 43.0 1 ° C. Based on this, there is no limit to the full width at half maximum. It is only the initial stage of the peak temperature. It is limited to 0.6 ~ 0.7 ° C and approximated, and the compound curve is separated into two to obtain the peak area. In this review, in order to shorten the time required for -10- (7) (7) 200426161 to converge (c ο nvergence), the information of the raw material powder is used, but it can also be obtained directly from the fibrous powder. Obtain the melting curve of the PTFE fibrous powder of the present invention, and perform a differential scanning calorimeter analysis on the temperature rise rate per minute. The peak area at the low temperature of the melting endothermic curve obtained is the total area of the peak area. 8 Above 8.5%, preferably above 92.0% and below 99.5%. In the case where the peak area at low temperature is less than 88.5% of the total peak area, insufficient cohesive force tends to cause the collapse of the molded product, and there is a tendency that the padding of the obtained paper is lacking. The area of the peaks at low temperature is too large, that is, two peaks (or shoulders) cannot be seen, and there are many cases where the forming of the papermaking can not become a better state, as described above. Generally, the forming methods such as paper making and compression molding are different from the molecular-level forming methods with uniform melting. The specific surface area of the raw material is closely related to its cohesive force, that is, the mechanical characteristics of the formed product. The larger the surface area, the better the mechanical properties of the formed product. The larger the contact area of each raw material is, the more the stress transmission point of the tissue is increased, and as a result, the mechanical characteristics of the entire tissue are improved. This is the same as the case of PTFE. The larger the specific surface area of the PTFE fibrous powder is, the larger its cohesive force is, and it is possible to obtain a material with excellent mechanical properties as the structure does not collapse. On the one hand, the more the fusion adhesion between PTFE fibrous powders occurs, the smaller the specific surface area of the papermaking will be, and it will show the rate of reduction of the specific surface area to a certain degree or more. It is also an important parameter for estimating the physical properties of papermaking. . Here, the same applies to the case of PTFE fibrous powder and its molded products. (8) (8) 200426161 The larger the specific surface area of PTFE fibrous powder is, the larger its cohesive force is, and the mechanical properties are obtained without collapse. Excellent molding. Therefore, in the present invention, the specific surface area of the PTFE fibrous powder is preferably 4.0 m2 / g or more, 5.0 m2 / g or more, and more preferably 8.5 M 2 / g or less. It should be noted that the specific surface area referred to here is the tritium measured by a nitrogen adsorption method. When the specific surface area is less than 40 m2 / g, insufficient cohesion force is liable to cause collapse during molding. Moreover, the molded product lacks uniformity, and the desired physical properties cannot be obtained. When the specific surface area is larger than 8.5m2 / g, the fibrous powder is easy to be densely packed. The net weight of papermaking (1 mesh = 4.3 05 5 g / m2) becomes larger, the air permeability is lowered, and it may not be visible. The tendency of cushioning. In order to make use of the characteristics of paper, the shape of the raw material powder is preferably fibrous. Generally, the fibrous shape can be expressed by the morphological coefficient. However, the irregular powder with a beard-like shape is used to display the aggregation of paper One of the forces may not be expressed in a fibrous form with respect to the form factor. In this case, a combination of specific surface area and form factor is required to determine whether it can be used as a raw material for making use of the properties of paper. In view of this, the so-called fiber # shape, because all or part of it is stretched by external forces, it is better to consider those who show anisotropy in terms of physical properties. For the raw material PTFE used in the present invention, a separate polymer of ethylene tetrafluoride (hereinafter referred to as TFE) may be used. TFE9 is 5 to 100 mole%, and is selected from the formula (I): CX2 = CY (CF2 ) nZ (I) (wherein x, Y, and z are the same or different and may be any hydrogen or fluorine atom, η is an integer of 1 to 5), and the formula (II): -12 -(10) (10) 200426161 First, the aforementioned raw material PTFE powder is put into the raw material feeding funnel from the feeder, and the raw material hopper is used to supply the raw PTFE powder from the stretching processing tank. The supply of the raw PTFE powder in the stretching treatment tank can be dropped due to its own weight. The raw PTFE powder can be mechanically processed. For the complete control of the shape of the PTFE fibrous powder obtained, the liquid or It is preferable to perform it with a highly fluid medium such as a gas. The stretching treatment tank is provided with stretching means (details will be described later), and the raw PTFE powder is stretched into a PTFE fibrous powder. Here, when the raw material PTFE powder is processed, the energy added to the PTFE powder in the step is controlled, and the degree of unfolding of the PTFE fibrous powder is preferably controlled. Then, with the classifying device, only the powder that can be fully stretched is selected and sent to the subsequent classifying device. The other powders are returned to the stretching treatment tank for further processing. Finally, the PTFE powder having a particle size of 5 // m or less is removed by a classification device (the measuring method is described later) to obtain the PTFE fibrous powder of the present invention. Each step will be described in detail below. In the step of supplying the aforementioned raw material PTFE powder from the raw material charging funnel to the stretching treatment tank, when a small particle diameter is used, the raw material PTFE powder is solidified in the feeding funnel, and it is difficult to drop and supply it by its own weight. In this case, a liquid such as water can be forcibly supplied to the stretching treatment tank. In the case where the obtained PTFE fibrous powder is not immediately supplied to the paper-making step for storage, since the use of a liquid medium is not appropriate, a gas such as dry air is used as a medium to supply the raw PTFE powder. However, the operation of the rotating body in the stretching treatment tank or the discharge of the raw PTFE powder after the stretching treatment is affected. Therefore, -14- (11) (11) 200426161 is not suitable. With these operations, PTFE fibrous powder with an average fiber length of 100 to 5000 / zm and an average form factor of 5 or more can be produced very efficiently. It is also preferable to use the frictional heat during stretching. This makes it easy to fibrillate and tends to obtain a powder having a relatively stable fiber length. Therefore, in the stretching means described above, it is preferable to perform the stretching treatment by using frictional force. As such a stretching means, for example, a hammer mill, a sieve mill, and the like are preferred. A device obtained by stretching a raw material powder by applying a shearing force to a rotating body only in one direction. During the aforementioned stretching treatment, the energy added to the PTFE powder by the self-stretching means is controlled to 10 ~ 200kcal / kg, which can prevent the occurrence of PTFE agglomerates. In particular, the energy is preferably controlled to 10 to 60 kcal / kg. The PTFE paper obtained from the PTFE fibrous powder thus obtained can be obtained with many entanglements between the fibrous powders, and a part of the PTFE paper having excellent cushioning properties can be obtained by thermally sticking the powders to each other. Here, when the energy added to the PTFE powder by the self-stretching method is less than 10 kcal / kg, the short fibrous powder increases and sufficient physical entanglement cannot be obtained. When the energy is more than 200 kcal / kg, it is difficult for the fibrous powder to thermally adhere to each other. Here, the aforementioned energy added to the PTFE powder by the self-stretching means during the stretching treatment is defined by the energy supplied by the stretching means. The energy of the supply and stretching means refers to the energy per lkg of the PTFE powder required to maintain the number of stretching rotations when the PTFE powder is stretched by the aforementioned stretching means, and can be self-stretched during stretching and idling. Find the difference between the currents of the means. When using -15- (12) (12) 200426161 to supply raw materials to the stretching treatment tank, the amount of heat supplied is based on room temperature below 40 ° C, which must be given by the temperature difference from the medium Calculate the heat. In the step of classifying after processing the PTFE powder, after the raw PTFE powder is processed, the classification operation is performed by a classifying device. This classification operation is performed so that the PTFE fibrous powder with insufficient stretching can be prevented from flowing out of the stretching treatment tank. Therefore, PTFE fibrous powder with an average fiber length of 100 to 5 000 // m can be obtained efficiently. In particular, the average fiber length is preferably 100 to 4 000 / zm. When the aforementioned average fiber length is less than 100 / zm, a part of the net-like base material falls off during paper making, which is a cause of pinholes. In addition, when the average fiber length exceeds 5 000 // m, it is difficult to manufacture paper with a uniform thickness because the fiber length is long. As for the classifying device, a screen for classifying can be used, and it is preferable to separate the powder with a predetermined size as the boundary. Further, removing PTFE fibrous powder having a particle diameter of 5 // m or less can improve the air permeability of the PTFE copy paper using the aforementioned powder paper, and it is preferable that φ is soft and has excellent cushioning properties. Furthermore, it is preferable to remove PTFE fibrous powder having a particle diameter of 10 m or less. Here, the aforementioned particle size is measured using a laser diffraction particle size distribution measuring device HELOS & RODOS system (manufactured by SYMPATEC), and the PTFE fibrous powder is dispersed and measured with compressed air of 3 bar. Particle size means 50% particle size. The average morphological coefficient of the PTFE fibrous powder is preferably 5 or more, and more preferably 10 or more. The upper limit 値 of the average morphological coefficient is not particularly limited. -16- (13) (13) 200426161 is preferably set to 10,000 or less. The aforementioned average morphological coefficient refers to a product obtained by dividing a fiber width by a fiber length. The aforementioned average morphology coefficient is smaller than 5, and it is difficult to peel off from the net-like substrate after calcination, and the surface smoothness or appearance (fluff, skewness) is poor, and it will become a bad paper after completion. The PTFE fibrous powder thus obtained was made into paper by the following method. First, the aforementioned PTFE fibrous powder is uniformly dispersed in water by a dispersant to form a paper stock. At this time, the organic material may be added to the paper material, and the inorganic filler material may be added. This paper stock is made on a substrate such as a mesh. Thereafter, it is dried and calcined to obtain PTFE paper. In particular, in the case where organic high-molecular reinforcing fibers are contained, a filter having a larger area can be provided without lining, thereby miniaturizing the filter unit. The thickness of the PTFE paper obtained from the paper making depends on its use, and is preferably 0.02 mm or more, 8.00 mm or less, more preferably 0.05 mm or more, 6.00 mm or less, and more preferably 0.1 mm or more and 4.00 mm or less. When the thickness is less than 0.02 mm, when used as a filter, the collection ability tends to be insufficient. If the thickness is larger than 8.00mm, the paper clip will deform due to its own weight, which will tend to impair the uniformity of pile w e i g h t. The surface smoothness of the PTFE paper obtained from the papermaking is preferably 10.5 µm or less, and more preferably 10.0 // m or less. When the surface smoothness is greater than 10.5 // m, scuffing during handling may tend to generate dust. In addition, the so-called surface smoothness here is the stylus-type surface roughness meter to calculate the arithmetic average roughness as described later. In addition, the permeability of the PTFE paper obtained from the paper making can be obtained according to (15) (15) 200426161 of the PTFE paper. In this way, in order to avoid compromising the high heat resistance of PTFE, the melting point is preferably 200 ° C or more, and more preferably 220 ° C or more. The components are not necessarily organic, and one or two or more corresponding materials can be selected according to the purpose. Examples of these include fibers such as polyparaphenylene benzazole, liquid crystalline polyester, aromatic polyamide pulp, glass, and carbon, but the present invention is not limited to these examples. The melting point is the number obtained by DSC method. As mentioned above, in order to maintain heat resistance, it is preferred that the corresponding material at the time of compounding has high heat resistance, and it is not necessary to have high heat resistance in applications where heat resistance is not particularly necessary. For example, in order to maintain the electrical characteristics of PTFE, in order to increase the strength of the papermaking, the cutting material of acrylic fiber, fiber-like materials, etc. can be selected as the corresponding materials. Polyamine, polyester, polyolefin, etc. can be selected as the corresponding materials. The papermaking paper of the present invention can be used for various applications because of its excellent heat resistance, and the aforementioned composite papermaking paper can be used depending on the situation, and suitable materials can be used. For example, when used as a core material for compression molding, it is possible to prevent the occurrence of abrasion between the sheet stamping molded article and the edge portion of the mold, and continuously ensure excellent release properties. When used as a filter material, in addition to being able to collect electricity in a static manner, it can also exhibit durability to strong acids and alkalis, and filterability at high temperatures. When it is used as a wire-wound coating material, because it has a hole in the inner part, it can exhibit more excellent insulation properties, and it can also be expected to have properties as a heat-insulating layer. When it becomes a tube-shaped strip, a tube-shaped seamless mesh can be used to make paper, which can be easily obtained with a seamless and excellent release property. -19- (16) (16) 200426161 seamless belt. If strength is necessary, it can be mixed with reinforcing fibers to make paper. When it is used as a positioning paper for solder reflow processing, solder adhesion is also reduced ', and workability can be expected to be further improved. When used as insulation paper ', it can prevent the adhesion of liquids and the like from the surrounding area, and it can safely protect the control unit of the pump unit and so on for a long time. In the circuit-based board that accompanies the speed of information processing and communication, the low electrical induction rate corresponding to the high frequency can be obtained. When applied to PTFE paper or mixed paper, it can not only exhibit excellent electrical characteristics, but also strengthen In the case of composite materials, sufficient dimensional stability and heat resistance φ can also be expected. As shown in Japanese Patent Application Laid-Open No. 2002-23 1 31, it is known to use PTFE paper as a cushioning material in a liquid crystal manufacturing production line. The cushioning properties required for other applications are various. The range requiring dimensional stability or abrasion resistance can be applied to mixed papermaking. Since the PTFE fibrous powder is very bulky, it is also very easy to mix with other materials in a dry state, so it is suitable as a raw material for composite moldings. In these applications, in the case of composite with other materials, if the weight fraction of Φ PTFE is less than 2%, the characteristics of PTFE cannot be fully exerted, and if it exceeds 98%, the effect of adding components other than PTFE cannot be fully obtained. Therefore, the weight fraction of components other than PTFE contained in the mixed molded product is preferably 2 to 98%, more preferably 4 to 96%, and particularly preferably 5 to 95%. Next, it will be further specifically described based on the embodiment of the present invention, but the present invention is not limited to this. In addition, each physical property 値 measured in the examples of the present invention is measured by the following method. -20- (17) (17) 200426161 (average fiber length) The powder is measured with an electron microscope, and the length in the fiber direction is 200 points or more based on the arithmetic mean. During the measurement, the length of 80 // m or less is not measured. (Average Morphology Coefficient) The powder is measured with an electron microscope, and the length in the direction of the obtained fiber is divided by φ the width of the fiber. The morphology coefficient of 200 points or more is obtained by arithmetic mean. At the time of measurement, it is not Measure the length below 80 // m. (Air permeability) Using a galare tester, PTFE paper was used to measure the time required for 300 mL of air to pass through a sharp hole of 1 cm 0. (Surface smoothness) The arithmetic average roughness was measured with a stylus-type surface roughness meter using PTFE paper. (Cushioning property) A compression tester was used to measure the compression workload of PTFE paper and the compression recovery workload of 10 round trips. The standard sample was expressed as the relative value at 100. The larger the cushion, the larger the number -21-(18) (18) 200426161. The standard sample refers to 60% of PTFE paper with a compression recovery workload / compressive workload x i 〇〇 (%). (Differential scanning type calorimetry) Measurement was performed using RPC-220 manufactured by Seiko instruments at a temperature rise rate of 5 ° C / min and a sample size of 3 mg. Refer to JIS-K7123. (Peak-to-peak area ratio) # Perform a differential scanning calorimeter analysis at a heating rate of 5 ° C per minute, and use the Gauss ia n-Lore nti-an curve for the DSC curve to separate it into two peak-to-peak curves. Divide the area of the peak chirp at the low temperature by the total peak chirp area to calculate the peak chirp area ratio. (Paper-making Thickness) This PTFE paper-making system is measured using a dial gauge Η type (a type having a pressure of 200 g or less). φ (Specific surface area) The specific surface area of the powder was evaluated by a nitrogen adsorption method using a biosorber manufactured by Yuasa Ionics Corporation as a standard battery. (Tensile strength) Using Orientic's universal testing machine (Tensilon) STA-1150, 15mm wide samples with a chuck distance of 100mm, -22-(20) (20) 200426161, can obtain a smooth surface . When the paper is cut again, it will not open at the end when cutting, and it can exert good cohesion. Table 1 Example 1 Example 2 Example 3 Manufacturing condition energy (kcal / kg) 3 7 52 70 Average fiber length of fibrous powder (mm) 0.4 1.5 .5 2.5 Average morphological coefficient 11 40 68 Peak-to-peak area ratio (%) 90.9 92.3 93.1 Specific surface area (m2 / g) 5.83 6.38 6.69 Thickness of PTFE paper (mm) 0.49 0.52 0.5 1 Surface smoothness (// m) 7 5 7 Air permeability (sec / cm 0 · 3 00mL) 9.5 7.0 6.5 Lining Cushion 92 105 1 10 Tensile strength (MPa) 1.2 1.5 1.6 Comparative Examples 1 to 3 The raw material p TF e powder was supplied to the stretching treatment tank with hot air at the temperature indicated in Table 2. The stretching treatment was obtained and implemented in addition to the stretching treatment. Example 1 was the same PTFE fibrous powder. The obtained PTFE fibrous powders each had an average fiber length, an average morphology coefficient, a peak-to-peak area ratio, and a specific surface area as shown in Table 2. -24- (21) 200426161 Next, paper was produced in the same manner as in Example 1 to obtain PTFE paper having a thickness of 0.47 to 0.51 mm. The surface smoothness, air permeability, cushioning property, and tensile strength of the obtained PTFE paper are shown in Table 2. The air permeability of the PTFE paper obtained in Comparative Example 1 was significantly deteriorated, and it was not suitable for filter applications at all. In addition, in any of the PTFE papers, an open line is generated during cutting, and it can be confirmed that the dimension retention of the cut portion is poor. Table 2 _ φ Comparative Example 1 Comparative Example 2 Comparative Example 3 Manufacturing conditions Energy is (kcal / kg) 8 102 95 Hot air temperature (° C) 55 82 80 Fibrous powder Average fiber length (mm) 0.2 5.5 5.2 Average form factor 4 17 1 145 Peak-to-peak area ratio (%) 85.0 嵚 1 ※ 1 Specific surface area (m2 / g) 3.0 7.1 7.0 Thickness of paper made of PTFE paper (mm) 0.47 0.50 0.5 1 Surface smoothness (// m) 11 2 1 23 Air permeability (sec / cm 0 · 3 OOmL) 14.5 4.5 5.5 Cushionability 75 84 89 Tensile strength (MPa) 0.5 ※ 2 0.9
※丨峰値位置完全在更低溫處偏移，造成解折疊完全 完成。 -25- (22) (22)200426161 ※2測定途中被溶解而無法測定 實施例4 在濕式製紙時相對於PTFE纖維狀粉末8重量份，除 了添加芳族聚醯胺紙漿（東麗公司製，Kevlar紙漿）2重 量份以外，其他與實施例1相同之操作可得到混合抄製紙 。測定自室温至2 5 0 °C之線熱膨脹係數時，爲〇.5ppm，可 確認優異熱尺寸安定性。 φ 産業上之利用可能性 依照本發明，可獲得具有均勻的物性分布，凝集性， 表面平滑性，均壓性，通氣性，粉塵捕集性，電特性，機 械特性優異之PTFE抄製紙。又，依照本發明，可有效率 地獲得平均纖維長100〜5000 // m，平均形態係數5以上之 PTFE纖維狀粉末。 • 【圖式簡單說明】 第1圖，係將P T F E粉末以差式掃瞄型熱量計分析所 得熔融吸熱曲線之例，及將此熔融吸熱曲線予以峰値分離 所得二條峰値曲線。 -26-※ 丨 The peak position is completely shifted at a lower temperature, resulting in complete unfolding. -25- (22) (22) 200426161 ※ 2 It was dissolved during measurement and cannot be measured. Example 4 8 parts by weight of PTFE fibrous powder during wet papermaking, except for the addition of aromatic polyurethane pulp (manufactured by Toray Co., Ltd.) , Kevlar pulp), except for 2 parts by weight, the same operation as in Example 1 can be used to obtain a mixed paper. When the linear thermal expansion coefficient was measured from room temperature to 250 ° C, it was 0.5 ppm, and excellent thermal dimensional stability was confirmed. φ Industrial Applicability According to the present invention, it is possible to obtain a PTFE paper with excellent physical distribution, cohesiveness, surface smoothness, pressure equalization, air permeability, dust collection property, electrical properties, and mechanical properties. Further, according to the present invention, a PTFE fibrous powder having an average fiber length of 100 to 5000 // m and an average morphology coefficient of 5 or more can be efficiently obtained. • [Schematic description] Figure 1 shows an example of the melting endothermic curve obtained by analyzing the P T F E powder with a differential scanning calorimeter, and two peak-to-peak curves obtained by peak-to-peak separation of this melting endothermic curve. -26-