201042105 六、發明說明： 【發明所屬之技術領域】 本發明關於一種瀝青系碳纖維織物、瀝青系碳短纖維 及該等製造方法，可適合使用作爲放熱材料、樹脂補強材 料。進一步詳細而言，關於一種瀝青系碳纖維織物、瀝青 系碳短纖維及其製造方法，與以往以熔吹法所製造的瀝青 系碳纖維織物或瀝青系碳短纖維相比，瀝青系碳纖維之平 〇 均纖維徑分布明顯較小，且兼具強度與彈性率的瀝青系碳 纖維所構成者。 【先前技術】 就瀝青系碳纖維的紡絲方法而言，可列舉以捲線機收 取由金屬紡嘴噴出的中間相瀝青，通常的紡絲延伸法；使 用熱風作爲霧化源的熔吹法；利用離心力收取中間相瀝青 的離心紡絲法等。其中，由於瀝青系碳纖維前驅物形態的 〇 控制、生產性高等原因，尤其以熔吹法爲適合使用（例如 專利文獻1、2、3)。該等瀝青系碳纖維，係藉著對在金 屬紡嘴附近熔融紡出的中間相瀝青吹送高速空氣，延伸的 細絲，於篩運機或多孔滾筒上，聚集成不織布狀，接著使 不織布不熔化、燒成而製造出來。以往熔吹法中，由金屬 嘴吹出的空氣，並非相對於纖維軸方向呈平行，係夾有某 個角度而吹出的方法。 以熔吹法所得到之瀝青系碳纖維，由於係以空氣將由 金屬紡嘴噴出的中間相瀝青拉長，因此與以捲線機進行收 -5- 201042105 取’通常的紡絲延伸法相比，絲直徑之分布變廣。因此， 在製造時的不熔化步驟’各纖維的氧附著量相異，會有最 終所.得到的纖維物性變得不均句的問題。另外，以空氣 將中間相瀝青拉長時’在通過毛細管的時候，已呈極度配 向的瀝青分子因爲空氣而造成配向被打亂，因此會有最終 所得到的碳纖維之機械特性降低的問題。 [先前技術文獻] 專利文獻 專利文獻1:日本特開平4-108150號公報 專利文獻2:日本特開2008-285797號公報 專利文獻3:日本特開2008-285795號公報 【發明內容】 [發明所欲解決之課題] 在以往的熔吹法中，絲直徑會發生變異。另外，由於 空氣使得構成瀝青系碳纖維前驅物的瀝青分子的配向變亂 ，因此最終所得到的碳纖維會有機械特性降低等的問題。 於是，本發明之目的爲提供一種瀝青系碳纖維織物， 係由與以往的熔吹法所得到之碳纖維相比，絲直徑之變異 小’且機械強度優異的瀝青系碳纖維所構成者；瀝青系碳 短纖維及其製造方法。 [用於解決課題之方法] 本發明係關於一種瀝青系碳纖維織物’係由平均纖維 -6 - 201042105 徑爲5〜20μιη、平均纖維徑之CV値爲3〜8%，拉伸彈性 率爲150〜lOOOGPa，且拉伸強度爲2.5〜5GPa的瀝青系 碳纖維所構成者。 並且，本發明還關於一種瀝青系碳短纖維，其係將上 述瀝青系碳纖維織物進一步加以粉碎並且燒成所得到者。 本發明之瀝青系碳纖維織物，較適合由瀝青系碳纖維 織物之製造方法所得到，係由（1)對於在紡絲孔內的熔 0 融黏度爲大於5Pa*s未達100Pa‘s (大於5 0poise而未達 lOOOpoise )之中間相瀝青，以與紡絲方向平行之空氣噴流 加以牽引同時進行紡絲，製造長纖維所構成之瀝青系碳纖 維前驅物織物的步驟、（2 )在氧化性氣體環境下使瀝青 系碳纖維前驅物織物不熔化，製造瀝青系不熔化纖維織物 的步驟、（3 )將瀝青系不熔化纖維織物燒成的步驟所構 成者。 另外，在經過可得到瀝青系碳纖維織物的步驟（1 ) 〇 〜（3)之後，藉著（4)粉碎及（5)燒成，可適當地得 到本發明之瀝青系碳短纖維。 [發明之效果] 本發明之瀝青系碳纖維織物及瀝青系碳短纖維，係與 以往之以熔吹法所製造的瀝青系碳纖維相比，構成織物的 瀝青系碳纖維絲直徑的變異明顯較小，且機械強度優異， 進一步可提供均質的機械特性、熱特性、電氣特性等諸物 性。 201042105 【實施方式】 本發明之瀝青系碳纖維織物，構成其之瀝青系碳纖維 ，與以往之以熔吹法所製造的瀝青系碳纖維相比，絲直徑 的變異較小，且機械強度優異，進一步可提供均質的機械 特性、熱特性、電氣特性等諸物性。 [瀝青系碳纖維織物] 構成本發明之瀝青系碳纖維織物的瀝青系碳纖維，以 光學顯微鏡觀測到的平均纖維徑爲5〜2 0 μιη。平均纖維徑 在5 μηι以下的情況，例如藉由粉碎製成瀝青系碳短纖維而 與基材複合時，塡料的數目會變多，因此基材/塡料混合 物之黏度變高，變得難以成形。相反地，平均纖維徑若超 過20μιη，則由於在與基材複合時，塡料的數目變少，因 此塡料彼此變得難以接觸，製成複合材時變得難以發揮出 有效的熱傳導效果。平均纖維徑之較佳範圍爲7〜15 μηι。 另外，構成本發明之瀝青系碳纖維織物的瀝青系碳纖 維，以光學顯微鏡觀測到的瀝青系碳纖維的纖維徑分散相 對於平均纖維徑的百分率（CV値）爲3〜8%。由於CV値 爲3〜8 % ’製造步驟之不熔化之中，在各纖維的氧附著量 達到均勻，最終所得到的碳纖維之物性變得均勻，可得到 具有均勻性能的複合材。CV値小於3 %時，由於纖維徑極 爲一致，因此進入塡料間隙的小尺寸塡料的量變少，在與 基材複合時，會變得難以形成緻密的充塡狀態，就結果而 -8- 201042105 言，會有變得難以得到高性能複合材的情形。CV値大於 8 %時，在不熔化的時候，氧附著量難以成爲均勻。CV値 宜爲4〜7 %。 構成本發明之瀝青系碳纖維織物的瀝青系碳纖維的拉 伸彈性率，係在 150〜lOOOGPa之範圍。未達 150GPa之 情況下，由於瀝青系碳纖維之結晶性低，因此織物的耐久 性亦降低，故爲不佳。另一方面，在超過l〇〇〇GPa的情況 0 下，由於瀝青系碳纖維的伸度變小，因此織物的操作性降 低，故爲不佳。構成織物的瀝青系碳纖維，其拉伸彈性率 之較佳範圍爲 200〜800GPa，更適合的範圍爲 300〜 700GPa。另外，構成本發明之織物的瀝青系碳纖維，其拉 伸強度在2.5〜5GPa之範圍。在未達2.5GPa之情況下， 由於瀝青系碳纖維的伸度低，因此織物的操作性降低，故 爲不佳。另一方面，在超過5GPa的情況下，由於瀝青系 碳纖維之結晶性會降低，而由於瀝青系碳纖維之結晶性低 〇 ，因此織物的耐久性亦降低，故爲不佳。拉伸強度之較佳 範圍爲2.7〜4.8GPa。 本發明之瀝青系碳纖維織物，係藉著集合至少5根以 上的瀝青系碳纖維束隨機纏繞而形成者。因此，本發明之 瀝青系碳纖維織物在進行針扎處理時，瀝青系碳纖維束具 有容易附在針上這樣的特徵。因此，在織物經過交叉纏繞 (c r 〇 s s w r a ρ )的情況，與以往的以熔吹法所製造的織物 相比，在針扎後所得到的氈的層間剝離強度會提升。 201042105 [瀝青系碳纖維織物之製造方法] 接下來，關於本發明之瀝青系碳纖維織物適合的製造 方法，依序對各步驟作說明。 [原料之中間相瀝青] 就歷青系碳纖維之原料而言，係以中間相瀝青爲佳， 中間相瀝青的中間相率，係至少90%以上，較佳爲95 %以 上’更佳爲99%以上。另外，中間相瀝青的中間相率，可 藉著對於處在熔融狀態的瀝青以偏光顯微鏡進行觀察來確 認。就中間相瀝青之原料而言，可列舉例如萘或菲這種縮 合多環烴化合物、石油系瀝青或煤碳系瀝青這種的縮合雜 環化合物等。其中尤其以萘或菲這種縮合多環烴化合物爲 佳。 更進一步就原料瀝青的軟化點而言，係以2 3 (TC以上 ’ 3 40 °C以下爲佳。瀝青系碳纖維前驅物之不熔化處理， 有必要以低於軟化點的低溫來處理。因此，軟化點如果低 於23 0 °C，則有在至少未達軟化點的低溫進行不熔化處理 的必要，就結果而言，不熔化需要長時間，故爲不佳。另 一方面，軟化點若超過34(TC，則瀝青變得容易發生熱分 解，所產生的氣體會在系統中造成氣泡產生等的問題發生 ，故爲不佳。軟化點的較佳範圍爲25 0 °C以上32〇°C以下 ，更佳爲2 6 0 °C以上3 1 0 °C以下。另外，原料瀝青的軟化 點，可藉由Mettler法求得。亦可將兩種以上原料瀝青適 當地組合而使用。所組合出的原料瀝青中間相率，係以至 -10- 201042105 少90%以上爲佳，而軟化點係以23 0°C以上340T：以下者 爲佳。 [(1 )製造瀝青系碳纖維前驅物織物的步驟] 本發明之製造方法中的紡絲方法，即爲所謂的熔融紡 絲法，而最大的特徵爲：對於中間相瀝青，以與紡絲方向 平行之空氣噴流加以牽引同時進行紡絲。瀝青系碳纖維原 0 料的中間相瀝青，係分子量相異的多環芳香族分子之集合 體，而剛紡出之後的碳纖維前驅物非常脆。因此，在熔吹 法之中，所紡出的碳纖維前驅物因爲風力而被切斷，會以 短纖維化的狀態聚集成不織布狀。相對於此，在本發明的 方法之中，係將中間相瀝青以與紡絲方向平行之空氣噴流 加以牽引同時進行紡絲。因此，並沒有往纖維剖面方向的 空氣所造成的應力施加，實際的瀝青系碳纖維前驅物，係 以長纖維的狀態而形成織物。空氣噴流只要是與紡絲方向 Q 實際上呈平行即可。另外，本發明所提到的長纖維，係意 指纖維長1 m以上之纖維，織物係意指不織布狀之物。 在紡絲孔內的熔融黏度係以大於5 P a · s未達1 OOP a . s (大於50poise而未達1 OOOpoise )爲佳。在紡絲孔內的熔 融黏度若未達5Pa · s，則以與紡絲方向平行之空氣噴流牽 引中間相歷青時，由於中間相瀝青沒有黏性，因此會因爲 牽引而發生斷絲，故爲不佳。另外，如果一旦發生斷絲， 則由金屬紡絲嘴呈棒狀擠壓出的中間相瀝青，在受到空氣 噴流牽引前爲止，絲直徑會變粗’而表示絲直徑變異指標 -11 - 201042105 的CV値變大，故爲不佳。另一方面，若超過ioopa.s， 則由於中間相瀝青的黏性高，因此，無法充分地牽引由金 屬紡絲嘴呈棒狀擠壓出的中間相瀝青，絲直徑會變粗。因 此’在接下來的不熔化處理步驟需要很多時間，造成生產 性降低’故爲不佳。在紡絲孔內的熔融黏度之較佳範圍， 係大於l〇Pa . s未達 50Pa . s (大於 l〇〇p〇ise而未達 5 OOpoise ) 〇 形成瀝青系碳纖維前驅物的紡絲噴嘴之形狀，爲任何 一種形狀皆可。通常使用呈正圓狀者，而即使適當地使用 橢圓等奇特形狀的噴嘴也不會有任何問題。就噴嘴孔之長 度（LN )與孔徑（DN )之比（LN/DN )而言，係以2〜20 之範圍爲佳。LN/DN若超過20，則對通過噴嘴的中間相 瀝青會施加強的剪應力，纖維剖面呈現出放射狀構造。呈 現出放射狀構造的現象，石墨化的過程中在纖維剖面會有 發生破裂的情形’而有造成機械特性降低的情形，故爲不 佳。另一方面’在LN/DN未達2的情況，無法對原料瀝 青施以剪切’就結果而言，變成瀝青分子配向低的瀝青系 碳纖維前驅物。因此’即使實施石墨化，也無法充分地提 高石墨化度’而難以提升熱傳導性，爲不佳。爲了達到兼 顧機械強度與熱傳導性，有必要對中間相瀝青施以適度的 剪切。因此’噴嘴孔長度（LN )與孔徑（DN )之比（ LN/DN ) ’係以2〜20之範圍爲佳，進一步以3〜12之範 圍爲特佳。另外’亦可在噴嘴正上方，適當地插入像是能 擾亂中間相瀝青的流動這樣的模具。 -12- 201042105 在以往熔吹法的金屬紡嘴，係具有由噴嘴孔附近吹送 空氣用的流通路，這會造成金屬紡嘴耐壓降低、且減少金 屬紡嘴設計的自由度、無法設置多個噴嘴孔等問題。然而 ，在此方法中，沒有必要在噴嘴孔附近設置吹送空氣用的 流通路，而金屬紡嘴設計的自由度仍可提高。因此，與熔 吹法的金屬紡嘴相比，可增加噴嘴孔的數目，就結果而言 ，可期待能夠帶來生產性的提升。噴嘴孔的排列方式並無 Q 特別限制，而可例示以同心圓狀設置噴嘴孔的方法：以直 線狀設置多列噴嘴孔的方法等。 在本發明中，通過紡絲孔的中間相瀝青的剪切速率係 以大於eooos」未達300008^爲佳。通過紡絲孔的中間相 瀝青的剪切速率若未達6000^1，則有引起生產性明顯降 低的情形。另一方面，若超過3 0000S·1，則通過毛細管的 中間相瀝青會產生嚴重的滑動，而有容易呈現放射狀構造 (會成爲碳纖維破裂的原因）的傾向。通過紡絲孔的中間 Q 相瀝青的剪切速率之較佳範圍，係7000〜20000s·1之範圍 〇 在本發明中，係以將熔融紡出的中間相瀝青，以3 0 0 〜1 0000m/分鐘之空氣噴流加以牽引爲佳。氣噴流的速度 若未達3 00m/分鐘，則碳纖維前驅物的絲直徑變粗，在接 下來的不熔化處理步驟需要很多時間，故爲不佳。另一方 面’若超過1 0000m/分鐘’則碳纖維前驅物之絲直徑變得 過細’在中間相瀝青延伸的過程中，有發生斷絲的情形。 空氣的風量’係於流量計所顯示的測定値，風速係將流量 -13- 201042105 除以吸引槍的剖面積而藉此算出。 風速的較佳範圍爲5 00〜6000m/分鐘，更佳爲 700〜 3 000m/分鐘。空氣噴流所使用的氣體並無特別限制，而由 成本效益與安全性的層面看來，則希望爲空氣。另外，爲 了要抑制碳纖維前驅物的斷絲，空氣噴流所使用的氣體溫 度，只要在中間相瀝青的軟化點以下即可，而由成本效益 與安全性的層面看來，係以室溫爲佳。 對於中間相瀝青，以與紡絲方向平行之空氣噴流加以 牽引同時進行紡絲，形成由長纖維所構成之瀝青系碳纖維 前驅物織物時，亦可透過紡絲筒。紡絲筒的形狀並未受到 特別限制，然而也會有容易帶靜電的情形，因此以實施防 靜電措施過後的筒爲佳。進一步以設置具備吸引機的捕集 機，捕集瀝青系碳纖維前驅物織物爲佳。 在步驟（1 )之中’對於中間相瀝青，以與紡絲方向 平行之空氣噴流加以牽引同時進行紡絲，形成由長纖維所 構成之瀝青系碳纖維前驅物織物，而對於形成織物之前的 長纖維而言，以X射線評估的瀝青系碳纖維前驅物之配向 度’係以8 4.5 %以上爲佳。以往的熔吹法中，由金屬紡嘴 吹出的空氣’並非相對於纖維軸方向呈平行，而係夾有某 個角度而吹出。因此’在金屬紡嘴內，已呈極度往纖維軸 方向配向的瀝青分子’因爲空氣所造成在纖維剖面方向的 應力施加’而使得瀝青分子的配向變亂。在本發明方法之 中’由於以與紡絲方向平行之空氣噴流牽引中間相瀝青， 因此空氣所造成在纖維剖面方向的應力施加幾乎不會發生 -14 - 201042105 。因此，與以熔吹法所製作的瀝青系碳纖維前驅物相比， 瀝青分子之配向度變高。以X射線評估的瀝青系碳纖維前 驅物之配向度未達84.5%之情況下，燒成的瀝青系碳纖維 之熱傳導性難以變高，而爲不佳。其原因推測爲，瀝青系 碳纖維前驅物之配向度如果很低，則在碳化過程中，六角 網面層的端面彼此無法順利連結，而無法長成大的結晶之 緣故。以X射線評估的瀝青系碳纖維前驅物之配向度之較 0 佳範圍爲8 5 %以上，更佳爲8 5.5 %以上。 另外，在織物形成之前，往纖維軸方向拉伸並聚集在 一起的瀝青系碳纖維前驅物，可藉著例如在紡絲筒設置取 樣處並進行取樣而取得。 以與紡絲方向平行之空氣噴流將中間相瀝青加以牽引 同時進行紡絲’會形成由瀝青系碳纖維前驅物所構成之長 纖維，而此瀝青系碳纖維前驅物，會被金屬網等輸送帶捕 集，成爲瀝青系碳纖維前驅物織物。此時，可藉由輸送帶 〇 搬運速度，調整成任意的基重，而亦可因應必要，藉由交 叉纏繞等方法使其層合。瀝青系碳纖維前驅物織物的基重 ’考慮到生產性以及步驟安定性，係以150〜.1 000g/m2爲 佳。另外’由於瀝青系碳纖維前驅物織物，係對於中間相 瀝青’以與紡絲方向平行之空氣噴流加以牽引同時進行紡 絲’因此藉著集合至少5根以上的瀝青系碳纖維前驅物束 隨機纏繞，而成爲不織布。 [(2)製造瀝青系不熔化纖維織物的步驟] 以如此的方式所得到之瀝青系碳纖維前驅物織物，係 -15- 201042105 以周知的方法進行不熔化處理，製成瀝青系不熔化纖維織 物。瀝青系不熔化纖維織物的不熔化，係在氧化性氣體環 境下實施，而此處的氧化性氣體，係意指空氣，或者可由 瀝青系碳纖維前驅物奪取電子的氣體與空氣之混合氣體。 就可由瀝青系碳纖維前驅物奪取電子的氣體而言，可例示 臭氧、碘、溴、氧等。然而若考慮安全性、便利性、成本 效益，則瀝青系碳纖維前驅物織物的不熔化，會特別希望 是空氣中實施。另外，以批次處理、連續處理之任一種來 處理皆可，而若考慮生產性，則希望爲連續處理。不熔化 處理，係在150〜350 °C之溫度，藉著施以一定時間的熱處 理而完成。較佳溫度範圍爲160〜3 40t。昇溫速度適合使 用1〜1 (TC /分鐘，連續處理之情況，藉著使其依序通過設 定爲任意溫度的多個反應室，可達成上述昇溫速度。昇溫 速度之較佳範圍，若考慮生產性以及步驟安定性，則爲3 〜9°C /分鐘。 在本發明方法之中，係以藉由上述操作而使6.2〜 7.8 wt%之範圍的氧附著於瀝青系不熔化纖維織物爲佳。於 瀝青系不熔化纖維織物的氧附著量若未達6_2wt%，則接 下來的碳化步驟之中，在纖維間會有發生熔接的情形。另 一方面，氧附著量若超過7.8 w t %，則最終所得到之瀝青 系碳纖維之石墨化性降低，有引起熱傳導性降低的情形。 於瀝青系不熔化纖維織物的氧附著量，其較佳範圍係在 6 · 5〜7 · 5 w t %之範圍。另外，於瀝青系不溶化纖維織物的 氧附著量，可藉元素分析而求得。 -16- 201042105 [(3 )製造瀝青系碳纖維織物的步驟] 接著將不熔化纖維織物燒成，得到瀝青系碳纖維織物 。瀝青系不熔化纖維在未達200 0°C的燒成，係以在真空中 ，或在使用了氮、氬、氪等惰性氣體的非氧化性環境中實 施爲佳。瀝青系不熔化纖維的未達2000 °C的燒成，係以批 次處理、連續處理之任一種來進行處理皆可，而如果考慮 Q 到生產性，則希望爲連續處理。在超過2 0 0 0 °C的燒成之中 ，由於環境氣體引起電離，因此以使用氬、氪等惰性氣體 爲佳。另外，爲了得到本發明之瀝青系碳纖維織物的較適 合的燒成溫度爲1 000 °C以上，較佳爲1 300°c以上，更佳 爲1 5 0 0 °c以上。 [瀝青系碳短纖維] 藉著將本發明之瀝青系碳纖維織物粉碎成所希望的纖 〇 維長度，可得到瀝青系碳短纖維。較適宜的是藉著將本發 明之瀝青系碳纖維織物粉碎成所希望的纖維長度，進一步 以100 0°c〜3 40 0°c進行燒成，可得到本發明之瀝青系碳短 纖維。亦即經過得到本發明之瀝青系碳纖維織物的步驟（ 1)〜（3)之後，藉著（4)粉碎及（5)燒成，可得到本 發明之瀝青系碳短纖維。 亦即本發明包含一種瀝青系碳短纖維之製造方法，係 (1 )對於在紡絲孔內的熔融黏度爲大於5Pa. s未達1 oop a • s的中間相瀝青，以與紡絲方向平行之空氣噴流加以牽引 -17- 201042105 同時進行紡絲’製造由長纖維所構成之瀝青系碳纖維前驅 物織物的步驟、（2 )在氧化性氣體環境下使瀝青系碳纖 維前驅物織物不熔化，製造瀝青系不熔化纖維織物的步驟 、（3 )將瀝青系不熔化纖維織物燒成、（4 )對所得到之 瀝青系碳纖維織物進行粉碎處理，進一步以（5) 1000 °C 〜3 4 0 0 °C燒成。 在瀝青系碳短纖維之製造方法中，係以將在（3)中 的燒成溫度定爲600〜1 200°C者爲佳。瀝青系不熔化纖維 織物之燒成溫度未達600°C之情況下，由於構成瀝青系不 熔化纖維織物的瀝青系不熔化纖維之機械強度明顯很低， 因此經過接下來的粉碎處理之後，會無法維持纖維形狀， 故爲不佳。另一方面，瀝青系不熔化纖維織物之燒成溫度 若超過1 200°C，則經過接下來的粉碎處理之後，會有纖維 沿著纖維軸方向裂開的傾向。粉碎處理前之瀝青系不熔化 纖維織物燒成溫度之較佳範圍爲650〜950 °C。 將不熔化纖維織物燒成之後，實施切斷、破碎、粉碎 等處理，而亦可進一步依照情況實施分級處理。處理方式 係因應所希望的纖維長度來選定，而切斷方面，適合使用 斷頭台式、單軸、雙軸以及多軸旋轉式等切斷機；破碎及 粉碎方面，適合使用利用衝撃作用的鎚式、銷式、球式、 珠式及棒式；利用粒子彼此的衝撞的高速旋轉式；利用壓 縮、撕裂作用的滚筒式、錐式及螺旋式等破碎機、粉碎機 等。爲了得到所希望的纖維長，亦可採用多種或複數機種 來構成切斷與破碎 '粉碎。處理環境爲濕式、乾式之任一 -18- 201042105 種皆可。在分級處理方面，適合使用振動篩式、離心分離 式、慣性力式、過濾式等分級裝置等。所希望的纖維長， 不僅可藉由機種的選定而得，還可藉由控制旋轉體、旋轉 刀刃等的轉速、供給量、刀刃間隙、系統內滯留時間等而 可得到。另外，在使用分級處理之情況中，所希望的纖維 長，亦可藉由調整篩網孔徑等而得到。 接著以1〇0〇°C〜3400°c將所得到之粉碎物加以燒成， 0 藉此可製造瀝青系碳短纖維。燒成溫度係以2500〜3 2001 爲佳。 本發明之瀝青系碳短纖維，其平均纖維徑爲5〜20 μπι ’平均纖維徑之CV値爲3〜8%，數目平均纖維長爲1〇〜 ΙΟΟΟμηι。平均纖維徑之較佳範圍爲7〜ι5μπι。CV値宜爲 4〜7%。數目平均纖維長的適合範圍爲3〇〜35〇μπι。 另外’以X射線繞射法所求得石墨層的面間隔（d002 値）爲0.3366nm以下’由厚度方向測到的微晶大小（Lc 〇 )爲2〇nm以上者爲佳。do 〇2値係意指構成石墨的石墨層 的面間隔’石墨的理論値爲〇 · 3 3 5 4nm，其係成爲實際的下 限値’愈接近石墨的理論値0.3 3 5 4 n m，可說是石墨化性愈 高，然而以人工的方法製造如此的高石墨化性碳纖維，是 極爲困難的事情。 以X射線繞射法所求得石墨層之面間隔（d〇〇2値） 愈接近0.33 54nm，石墨化愈高，變得容易表現出熱傳導效 果，而成爲熱傳導性高的瀝青系碳纖維。以χ射線繞射法 所求彳守的d002値，其適宜的値爲〇 3 3 62nm以下，更佳爲 -19- 201042105 〇-3 3 6〇nm以下。瀝青系碳纖維之石墨結晶之由厚度方向測 到的微晶大小（Lc )之較佳範圍爲40nm以上，更佳爲 7 0nm以上，上限實際爲2〇〇nm以下。本發明之瀝青系碳 短纖維’可使用於樹脂補強劑、熱傳導性塡料等。 [實施例] 以下藉由實施例對本發明作更進一步具體地說明，而 本發明完全不會受其限定。另外’實施例中的各値，以依 照以下方法求得。 (1)瀝青系碳纖維之平均纖維徑與纖維徑分散 在光學顯微鏡下，使用刻度尺測定6 0根瀝青系碳纖 維’由其平均値求得。另外，CV値，係以所得到之平均 纖維徑（Ave )與纖維徑之偏差（S)的比率，藉由下式決 定。 CV = S/Avex100 此處，S = Τ' ( ( Σ X — Ave) 2/n) ，X 係觀測値、η 係觀測數。 (2)瀝青系不熔化纖維織物之氧附著量 瀝青系不熔化纖維織物之氧附著量，係以 CHNS-O Analyzer ( Thermo ELECTRON CORPRATION 製 FLASH EA 1112 Series)進行評估。 (3 ) d002 ' Lc、La 之評估 -20- 201042105 d002與來自八角網面之厚度方向的微晶大小，係使用 由（002)面得到的繞射線而求得，來自六角網面成長方 向的微晶大小，係使用由（i〗〇 )面得到的繞射線而求得 。另外’求侍的方法’係依據學振法（Gakushin method) 來實施。 (4 )熔融黏度之測定 〇 通過毛細管的瀝青黏度，係使用毛細管流變儀 CAPILOGRAPH 1D (東洋精機製作所股份有限公司）決定 。另外’通過毛細管的瀝青剪切速率，係藉下式求 出。[Technical Field] The present invention relates to a pitch-based carbon fiber woven fabric, a pitch-based carbon short fiber, and the like, and can be suitably used as a heat releasing material or a resin reinforcing material. More specifically, a pitch-based carbon fiber woven fabric, a pitch-based carbon short fiber, and a method for producing the same, compared with a pitch-based carbon fiber woven fabric or a pitch-based carbon short fiber produced by a melt-blown method in the past, a pitch-based carbon fiber slab It is composed of pitch-based carbon fibers with a small average fiber diameter distribution and a combination of strength and modulus of elasticity. [Prior Art] The spinning method of the pitch-based carbon fiber includes a mesophase pitch which is ejected from a metal spun nozzle by a winding machine, a usual spinning extension method, and a melt blowing method using hot air as an atomizing source; The centrifugal spinning method of collecting mesophase pitch by centrifugal force. Among them, the melt blown method is suitably used because of the 〇 control of the form of the pitch-based carbon fiber precursor, and high productivity (for example, Patent Documents 1, 2, and 3). The pitch-based carbon fibers are obtained by blowing high-speed air to the mesophase pitch melt-spun near the metal spun, and extending the filaments onto the sieve machine or the perforated drum to form a non-woven fabric, and then the non-woven fabric is not melted. It is made by firing. In the conventional melt blowing method, the air blown from the metal nozzle is not parallel to the fiber axis direction, and is blown at a certain angle. The pitch-based carbon fiber obtained by the melt-blown method is elongated by the mesophase pitch which is ejected from the metal spout by air, and is compared with the conventional spinning extension method of the reeling machine--5-201042105. The distribution has become wider. Therefore, in the non-melting step at the time of manufacture, the amount of oxygen attached to each of the fibers differs, and there is a problem that the obtained fiber properties become uneven. Further, when the mesophase pitch is elongated by air, when the capillary molecules which have been extremely aligned are passed through the capillary, the alignment is disturbed by the air, so that the mechanical properties of the finally obtained carbon fiber are lowered. [Prior Art] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-285797 (Patent Document No. JP-A-2008-285797) Problem to be solved] In the conventional melt blowing method, the wire diameter is mutated. Further, since the air aligns the alignment of the pitch molecules constituting the pitch-based carbon fiber precursor, the carbon fiber finally obtained has a problem that the mechanical properties are lowered. Accordingly, an object of the present invention is to provide a pitch-based carbon fiber woven fabric which is composed of a pitch-based carbon fiber having a small variation in wire diameter and excellent mechanical strength as compared with a carbon fiber obtained by a conventional melt-blowing method; Short fibers and methods of making same. [Means for Solving the Problem] The present invention relates to a pitch-based carbon fiber fabric which has an average fiber -6 - 201042105 diameter of 5 to 20 μm, an average fiber diameter of CV 値 of 3 to 8%, and a tensile modulus of 150. It is composed of pitch-based carbon fibers of ~100OGPa and a tensile strength of 2.5 to 5 GPa. Further, the present invention relates to a pitch-based carbon short fiber obtained by further pulverizing and firing the above-mentioned pitch-based carbon fiber woven fabric. The pitch-based carbon fiber woven fabric of the present invention is more suitable for the production method of the pitch-based carbon fiber woven fabric, and is (1) for the melt-melting viscosity in the spinning hole is more than 5 Pa*s and less than 100 Pa's (greater than 5) 0poise and less than 100 poise) mesophase pitch, which is drawn while being blown by an air jet parallel to the spinning direction, to produce a pitch-based carbon fiber precursor fabric composed of long fibers, and (2) in an oxidizing gas environment The step of causing the pitch-based carbon fiber precursor fabric to be infusible, the step of producing a pitch-based infusible fiber fabric, and (3) the step of firing the pitch-based infusible fiber fabric. Further, after the steps (1) to (3) of obtaining the pitch-based carbon fiber woven fabric, the pitch-based carbon short fibers of the present invention can be suitably obtained by (4) pulverization and (5) baking. [Effects of the Invention] The pitch-based carbon fiber woven fabric and the pitch-based carbon short fiber of the present invention have a significantly smaller variation in the diameter of the pitch-based carbon fiber constituting the woven fabric than the conventional pitch-based carbon fiber produced by the melt-blown method. Moreover, it is excellent in mechanical strength, and further provides physical properties such as uniform mechanical properties, thermal properties, and electrical properties. [Embodiment] The pitch-based carbon fiber woven fabric of the present invention comprises the pitch-based carbon fiber, and the variation in the wire diameter is smaller than that of the conventional pitch-based carbon fiber produced by the melt-blown method, and the mechanical strength is excellent, and further Provides physical properties such as homogeneous mechanical properties, thermal properties, and electrical properties. [Pitch-based carbon fiber woven fabric] The pitch-based carbon fiber constituting the pitch-based carbon fiber woven fabric of the present invention has an average fiber diameter of 5 to 20 μm as observed by an optical microscope. When the average fiber diameter is 5 μm or less, for example, when the pitch-based carbon short fibers are pulverized and combined with the substrate, the number of the mash increases, so that the viscosity of the substrate/draft mixture becomes high and becomes Difficult to form. On the other hand, when the average fiber diameter exceeds 20 μm, the number of the materials becomes small when they are combined with the substrate, so that the materials become difficult to contact each other, and it becomes difficult to exert an effective heat conduction effect when the composite material is formed. The average fiber diameter is preferably in the range of 7 to 15 μηι. In addition, the pitch-based carbon fibers constituting the pitch-based carbon fiber woven fabric of the present invention have a fiber diameter dispersion (CV 値) of the pitch-based carbon fibers observed by an optical microscope of 3 to 8%. Since the CV 値 is 3 to 8 % of the incomplete melting step, the amount of oxygen attached to each fiber is uniform, and the physical properties of the finally obtained carbon fiber are made uniform, whereby a composite material having uniform properties can be obtained. When the CV 値 is less than 3%, since the fiber diameter is extremely uniform, the amount of the small-sized mash that enters the mash gap becomes small, and when it is compounded with the substrate, it becomes difficult to form a dense filling state, and as a result, -8 - 201042105 It is said that it will become difficult to obtain high-performance composite materials. When CV 値 is more than 8%, it is difficult to make the oxygen adhesion amount uniform when it is not melted. CV値 should be 4 to 7%. The tensile modulus of the pitch-based carbon fibers constituting the pitch-based carbon fiber woven fabric of the present invention is in the range of 150 to 100 GPa. In the case of less than 150 GPa, since the crystallinity of the pitch-based carbon fiber is low, the durability of the fabric is also lowered, which is not preferable. On the other hand, in the case of more than 10 〇〇〇 GPa, since the elongation of the pitch-based carbon fiber is small, the workability of the woven fabric is lowered, which is not preferable. The pitch-based carbon fiber constituting the woven fabric preferably has a tensile modulus of 200 to 800 GPa, more preferably 300 to 700 GPa. Further, the pitch-based carbon fibers constituting the woven fabric of the present invention have a tensile strength in the range of 2.5 to 5 GPa. In the case of less than 2.5 GPa, since the elongation of the pitch-based carbon fiber is low, the workability of the fabric is lowered, which is not preferable. On the other hand, when it exceeds 5 GPa, the crystallinity of the pitch-based carbon fiber is lowered, and since the crystallinity of the pitch-based carbon fiber is low, the durability of the woven fabric is also lowered, which is not preferable. The tensile strength is preferably in the range of 2.7 to 4.8 GPa. The pitch-based carbon fiber woven fabric of the present invention is formed by randomly winding at least five or more pitch-based carbon fiber bundles. Therefore, in the pitch-based carbon fiber woven fabric of the present invention, the pitch-based carbon fiber bundle has a feature that it is easy to attach to the needle. Therefore, when the fabric is cross-wound (c r 〇 s s w r a ρ ), the interlaminar peel strength of the felt obtained after the needle sticking is improved as compared with the conventional fabric produced by the melt blow method. 201042105 [Method for Producing Pitch-Based Carbon Fiber Fabric] Next, each step will be described in order of a suitable manufacturing method of the pitch-based carbon fiber fabric of the present invention. [Mesophase pitch of raw materials] For the raw materials of the green carbon fiber, the mesophase pitch is preferred, and the mesophase ratio of the mesophase pitch is at least 90%, preferably 95% or more, and more preferably 99. %the above. Further, the intermediate phase ratio of the mesophase pitch can be confirmed by observing the asphalt in a molten state with a polarizing microscope. The raw material of the mesophase pitch may, for example, be a condensed heterocyclic compound such as naphthalene or phenanthrene, a petroleum-based pitch or a coal-carbon pitch. Among them, a condensed polycyclic hydrocarbon compound such as naphthalene or phenanthrene is preferred. Further, in terms of the softening point of the raw material pitch, it is preferably 2 3 (TC or more above 3 40 ° C. The infusibilization of the pitch-based carbon fiber precursor is necessary to be treated at a low temperature lower than the softening point. If the softening point is lower than 23 ° C, it is necessary to carry out the infusibilization treatment at a low temperature which does not reach the softening point. As a result, it takes a long time to melt, which is not preferable. On the other hand, the softening point If it exceeds 34 (TC), the pitch is likely to be thermally decomposed, and the generated gas may cause problems such as generation of bubbles in the system, which is not preferable. The softening point is preferably in the range of 25 ° C or more and 32 〇. It is more preferably 260 ° C or more and more than 301 ° C. The softening point of the raw material pitch can be determined by the Mettler method. Two or more kinds of raw material pitches can also be used in combination as appropriate. The intermediate phase ratio of the raw material pitch to be combined is preferably 90% or more to -10-201042105, and the softening point is 340T above 234 °C: (1) manufacturing of pitch-based carbon fiber precursors. Step of fabric] Spinning in the manufacturing method of the present invention The method is the so-called melt spinning method, and the biggest feature is that for the mesophase pitch, the air jet stream parallel to the spinning direction is drawn and simultaneously spun. The mesophase pitch of the pitch-based carbon fiber raw material is a collection of polycyclic aromatic molecules having different molecular weights, and the carbon fiber precursor immediately after spinning is very brittle. Therefore, in the melt blowing method, the spun carbon fiber precursor is cut by the wind, and The state of the short fiber is aggregated into a non-woven fabric. In contrast, in the method of the present invention, the mesophase pitch is drawn while being blown by the air jet parallel to the spinning direction. Therefore, there is no fiber profile. The stress caused by the air in the direction is applied, and the actual pitch-based carbon fiber precursor forms a fabric in a state of long fibers. The air jet may be substantially parallel to the spinning direction Q. Further, the present invention Long fiber means a fiber with a fiber length of 1 m or more, and a fabric system means a non-woven fabric. The melt viscosity in the spinning hole is greater than 5 P a · s. Up to 1 OOP a. s (greater than 50 poise but less than 1 OOOpoise). If the melt viscosity in the spinning hole is less than 5 Pa · s, the intermediate phase is drawn by the air jet parallel to the spinning direction. Since the mesophase pitch is not viscous, it may be broken due to the pulling, so it is not good. In addition, if the broken wire is broken, the mesophase pitch extruded from the metal spinning nozzle in the shape of a rod is subjected to air. Until the jet flow is pulled, the diameter of the wire will become thicker, and the CV of the wire diameter variation index -11 - 201042105 becomes larger, so it is not good. On the other hand, if it exceeds ioopa.s, the viscosity of the mesophase pitch is due to It is high, and therefore, the mesophase pitch extruded from the metal spinning nozzle in a rod shape cannot be sufficiently pulled, and the wire diameter becomes thick. Therefore, it takes a lot of time to cause a decrease in productivity in the subsequent infusible treatment step, which is not preferable. The preferred range of melt viscosity in the spinning orifice is greater than l〇Pa.s less than 50 Pa.s (greater than l〇〇p〇ise but less than 5 OOpoise) 纺 forming a spinning nozzle of a pitch-based carbon fiber precursor The shape can be any shape. Usually, a person who is in a perfect shape is used, and even if a nozzle having a strange shape such as an ellipse is used as appropriate, there is no problem. The ratio of the length (LN) of the nozzle hole to the diameter (DN) (LN/DN) is preferably in the range of 2 to 20. If the LN/DN exceeds 20, strong shear stress is applied to the mesophase pitch passing through the nozzle, and the fiber cross section exhibits a radial structure. A phenomenon in which a radial structure is exhibited, and a crack occurs in the fiber cross section during the graphitization process, and the mechanical properties are deteriorated, which is not preferable. On the other hand, in the case where the LN/DN is less than 2, it is impossible to apply shear to the raw material asphalt, and as a result, it becomes a pitch-based carbon fiber precursor having a low pitch of molecular molecules. Therefore, even if graphitization is carried out, the degree of graphitization cannot be sufficiently increased, and it is difficult to improve the thermal conductivity, which is not preferable. In order to achieve both mechanical strength and thermal conductivity, it is necessary to apply moderate shear to the mesophase pitch. Therefore, the ratio of the nozzle hole length (LN) to the aperture (DN) (LN/DN)' is preferably in the range of 2 to 20, and further preferably in the range of 3 to 12. Alternatively, a mold such as a flow capable of disturbing the flow of the mesophase pitch may be appropriately inserted directly above the nozzle. -12- 201042105 The metal spinning nozzle of the conventional melt-blowing method has a flow passage for blowing air near the nozzle hole, which causes a decrease in the pressure resistance of the metal nozzle, and reduces the degree of freedom in designing the metal nozzle, and cannot be provided in plurality. Problems such as nozzle holes. However, in this method, it is not necessary to provide a flow path for blowing air near the nozzle hole, and the degree of freedom in designing the metal spout can be improved. Therefore, the number of nozzle holes can be increased as compared with the metal spinning nozzle of the melt blowing method, and as a result, productivity improvement can be expected. The arrangement of the nozzle holes is not particularly limited, and a method of providing nozzle holes in a concentric manner can be exemplified: a method of arranging a plurality of rows of nozzle holes in a straight line. In the present invention, the shear rate of the mesophase pitch through the spinning holes is preferably greater than eooos" less than 300008^. If the shear rate of the mesophase pitch through the spinning hole is less than 6000^1, there is a case where the productivity is remarkably lowered. On the other hand, if it exceeds 30,000 S·1, the mesophase pitch passing through the capillary will cause severe sliding, and tends to have a radial structure (which may cause cracking of the carbon fiber). The preferred range of the shear rate of the intermediate Q-phase pitch through the spinning hole is in the range of 7000 to 20000 s·1. In the present invention, the mesophase pitch to be melt-spun is 300 to 10,000 m. The air jet of /min is preferably pulled. If the velocity of the gas jet is less than 300 m/min, the diameter of the carbon fiber precursor becomes thick, and the subsequent infusibilization treatment step requires a lot of time, which is not preferable. On the other hand, if it exceeds 10,000 m/min, the diameter of the carbon fiber precursor becomes too fine. In the process of extension of the mesophase pitch, breakage occurs. The air volume of the air is measured by the flow meter, and the wind speed is calculated by dividing the flow rate -13 - 201042105 by the cross-sectional area of the suction gun. The wind speed is preferably in the range of 50,000 to 6,000 m/min, more preferably 700 to 3,000 m/min. The gas used for the air jet is not particularly limited, but it is desirable from the perspective of cost effectiveness and safety. In addition, in order to suppress the broken filament of the carbon fiber precursor, the temperature of the gas used for the air jet may be less than the softening point of the mesophase pitch, and it is preferably room temperature from the perspective of cost effectiveness and safety. . In the case of the mesophase pitch, the air jet stream parallel to the spinning direction is drawn while being spun to form a pitch-based carbon fiber precursor fabric composed of long fibers, and also through the spinning drum. The shape of the spinning drum is not particularly limited, but there is a case where it is easy to carry static electricity, and therefore it is preferable to carry out the cylinder after the antistatic treatment. Further, it is preferable to collect a pitch-based carbon fiber precursor fabric by providing a trapper having a suction machine. In the step (1), 'for the mesophase pitch, the air jet parallel to the spinning direction is drawn while spinning, forming a pitch-based carbon fiber precursor fabric composed of long fibers, and long before forming the fabric. In terms of fibers, the orientation of the pitch-based carbon fiber precursors evaluated by X-rays is preferably 4.5% or more. In the conventional melt blowing method, the air ** blown out from the metal spun nozzle is not parallel to the direction of the fiber axis, and is blown at a certain angle. Therefore, in the metal spun, the pitch molecules which have been aligned in the direction of the fiber axis are disturbed by the stress applied in the fiber cross-sectional direction by the air. In the method of the present invention, since the mesophase pitch is pulled by the air jet parallel to the spinning direction, the stress applied by the air in the cross-sectional direction of the fiber hardly occurs -14 - 201042105. Therefore, the degree of alignment of the pitch molecules becomes higher than that of the pitch-based carbon fiber precursor produced by the melt blowing method. When the orientation of the pitch-based carbon fiber precursor evaluated by the X-ray is less than 84.5%, the thermal conductivity of the fired pitch-based carbon fiber is hard to be high, which is not preferable. The reason for this is presumed to be that if the orientation of the pitch-based carbon fiber precursor is low, the end faces of the hexagonal mesh layer cannot be smoothly connected to each other during the carbonization process, and it is impossible to grow into a large crystal. The alignment of the pitch-based carbon fiber precursors evaluated by X-rays is preferably more than 85%, more preferably more than 85.5%. Further, before the formation of the woven fabric, the pitch-based carbon fiber precursor which is stretched and gathered in the fiber axis direction can be obtained by, for example, setting a sample at the spinning drum and sampling. The mesophase pitch is drawn and simultaneously spun by an air jet parallel to the spinning direction, which will form a long fiber composed of a pitch-based carbon fiber precursor, and the pitch-based carbon fiber precursor will be caught by a metal mesh or the like. Set, become a pitch-based carbon fiber precursor fabric. In this case, the conveyance speed of the conveyor belt can be adjusted to an arbitrary basis weight, or it can be laminated by a method such as cross-winding if necessary. The basis weight of the pitch-based carbon fiber precursor fabric is preferably 150 to 1.1,000 g/m2 in view of productivity and step stability. In addition, 'because of the pitch-based carbon fiber precursor fabric, the mesophase pitch 'is pulled while being blown by the air jet parallel to the spinning direction', and thus is randomly wound by collecting at least 5 or more pitch-based carbon fiber precursor bundles. And become non-woven. [(2) Step of producing pitch-based infusible fiber fabric] The pitch-based carbon fiber precursor fabric obtained in such a manner is -15-201042105, which is infusible by a known method to prepare a pitch-based infusible fiber fabric. . The infusibilization of the pitch-based infusible fiber fabric is carried out in an oxidizing gas atmosphere, and the oxidizing gas herein means air or a mixed gas of gas and air which can take electrons from the pitch-based carbon fiber precursor. Examples of the gas which can take electrons from the pitch-based carbon fiber precursor include ozone, iodine, bromine, oxygen, and the like. However, in view of safety, convenience, and cost effectiveness, the infusibilization of the pitch-based carbon fiber precursor fabric is particularly desirable in air. Further, it may be handled by either batch processing or continuous processing, and if productivity is considered, continuous processing is desired. The non-melting treatment is carried out at a temperature of 150 to 350 ° C by applying heat treatment for a certain period of time. The preferred temperature range is from 160 to 3 40t. The temperature increase rate is preferably 1 to 1 (TC / min, continuous treatment), and the above temperature increase rate can be achieved by sequentially passing a plurality of reaction chambers set to an arbitrary temperature. The preferred range of temperature increase rate, if production is considered And the stability of the step is 3 to 9 ° C / min. In the method of the present invention, it is preferred that the oxygen in the range of 6.2 to 7.8 wt% is attached to the asphalt-based infusible fiber fabric by the above operation. If the oxygen adhesion amount of the asphalt-based infusible fiber fabric is less than 6-2 wt%, the subsequent carbonization step may cause fusion between the fibers. On the other hand, if the oxygen adhesion amount exceeds 7.8 wt%, Then, the graphitization property of the pitch-based carbon fiber finally obtained is lowered, and the thermal conductivity is lowered. The oxygen adhesion amount of the asphalt-based infusible fiber fabric is preferably in the range of 6 · 5 to 7 · 5 wt % In addition, the oxygen adhesion amount of the asphalt-based insoluble fiber fabric can be obtained by elemental analysis. -16 - 201042105 [(3) Step of producing pitch-based carbon fiber fabric] Next, the infusibilized fiber fabric is fired. To pitch-based carbon fiber fabrics. It is preferred that the pitch-based infusible fibers are calcined at less than 200 ° C in a non-oxidizing environment in a vacuum or in an inert gas such as nitrogen, argon or helium. When the pitch-based infusible fiber is not calcined at 2000 °C, it may be treated by either batch treatment or continuous treatment, and if Q to productivity is considered, continuous treatment is desired. In the firing at 0 ° C, ionization is caused by the ambient gas, so it is preferable to use an inert gas such as argon or helium. Further, a suitable firing temperature for obtaining the pitch-based carbon fiber woven fabric of the present invention is 1 000 °. C or more, preferably 1 300 ° C or more, more preferably 1 500 ° C or more. [Pitch-based carbon short fiber] By pulverizing the pitch-based carbon fiber fabric of the present invention into a desired fiber length, A pitch-based carbon short fiber can be obtained. Preferably, the pitch-based carbon fiber fabric of the present invention is pulverized to a desired fiber length, and further fired at 100 ° C to 3 40 ° ° C to obtain the present invention. Asphalt carbon short fiber. After the steps (1) to (3) of obtaining the pitch-based carbon fiber woven fabric of the present invention, the pitch-based carbon short fibers of the present invention can be obtained by (4) pulverization and (5) firing. That is, the present invention comprises a The method for producing a pitch-based carbon short fiber is (1) for a mesophase pitch having a melt viscosity in a spinning hole of more than 5 Pa·s not exceeding 1 oop a • s, which is towed by an air jet parallel to the spinning direction. -17- 201042105 Simultaneously spinning a step of producing a pitch-based carbon fiber precursor fabric composed of long fibers, and (2) not melting the pitch-based carbon fiber precursor fabric in an oxidizing gas atmosphere to produce pitch-based infusible fibers The step of woven fabric, (3) firing the asphalt-based infusible fiber fabric, and (4) pulverizing the obtained pitch-based carbon fiber woven fabric, and further firing at (5) 1000 ° C to 3400 ° C. In the method for producing a pitch-based carbon short fiber, it is preferred to set the firing temperature in (3) to 600 to 1 200 °C. When the firing temperature of the asphalt-based infusible fiber fabric is less than 600 ° C, since the mechanical strength of the asphalt-based infusible fiber constituting the asphalt-based infusible fiber fabric is remarkably low, after the subsequent pulverization treatment, It is not good to maintain the fiber shape. On the other hand, when the baking temperature of the pitch-based infusible fiber fabric exceeds 1,200 °C, the fiber tends to be split along the fiber axis direction after the subsequent pulverization treatment. The pitch of the asphalt which is not melted before the pulverization treatment is preferably in the range of 650 to 950 °C. After the infusibilized fiber fabric is fired, treatment such as cutting, crushing, and pulverization is carried out, and classification treatment may be further carried out according to circumstances. The treatment method is selected according to the desired fiber length, and the cutting machine is suitable for cutting machines such as broken head, single shaft, double shaft and multi shaft rotary type; for crushing and crushing, it is suitable to use hammer type using punching action. , pin type, ball type, bead type and rod type; high-speed rotary type that uses collision of particles; drum type, cone type and spiral type crusher, crusher, etc. which use compression and tearing action. In order to obtain the desired fiber length, a plurality of or a plurality of types of machines can be used to constitute the cutting and crushing. The treatment environment is either wet or dry. -18- 201042105 can be used. In the classification treatment, it is suitable to use a sizing device such as a vibrating screen type, a centrifugal separation type, an inertial force type, or a filtration type. The desired fiber length can be obtained not only by the selection of the model, but also by controlling the number of revolutions, the amount of supply, the blade gap, the residence time in the system, and the like of the rotating body, the rotating blade, and the like. Further, in the case of using the classification treatment, the desired fiber length can also be obtained by adjusting the mesh aperture or the like. Next, the obtained pulverized material is fired at 1 〇 0 ° ° C to 3400 ° C, whereby 0 can be used to produce pitch-based carbon short fibers. The firing temperature is preferably 2500 to 3 2001. The pitch-based carbon short fibers of the present invention have an average fiber diameter of 5 to 20 μm. The average fiber diameter has a CV 3 of 3 to 8%, and the number average fiber length is 1 〇 to ΙΟΟΟμηι. The average fiber diameter is preferably in the range of 7 to 5 μm. CV should be 4 to 7%. The suitable range of the number average fiber length is 3〇~35〇μπι. Further, the interplanar spacing (d002 値) of the graphite layer obtained by the X-ray diffraction method is 0.3366 nm or less. The crystallite size (Lc 〇 ) measured in the thickness direction is preferably 2 〇 nm or more. Do 〇2値 means the surface spacing of the graphite layer constituting graphite. The theoretical 値 of graphite is 〇·3 3 5 4nm, which is the actual lower limit 値' closer to the theoretical 値0.3 3 5 4 nm of graphite, it can be said that The higher the graphitization property, the artificially high-graphitizable carbon fiber is extremely difficult to manufacture. The surface spacing (d〇〇2値) of the graphite layer obtained by the X-ray diffraction method is as high as 0.33 to 54 nm, and the higher the graphitization, the easier the heat conduction effect is, and the carbon fiber having high thermal conductivity is formed. The d002 which is obeyed by the χ ray diffraction method has a suitable 値 of 3 3 62 nm or less, more preferably -19- 201042105 〇-3 3 6 〇 nm or less. The preferred range of the crystallite size (Lc) measured by the thickness direction of the graphite crystal of the pitch-based carbon fiber is 40 nm or more, more preferably 70 nm or more, and the upper limit is actually 2 〇〇 nm or less. The pitch-based carbon short fibers of the present invention can be used for a resin reinforcing agent, a thermally conductive coating or the like. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited at all. Further, each of the examples in the examples was obtained by the following method. (1) The average fiber diameter and the fiber diameter of the pitch-based carbon fiber were dispersed under an optical microscope, and 60 pitches of carbon fibers were measured by a scale to obtain the average. Further, CV値 is determined by the ratio of the obtained average fiber diameter (Ave) to the fiber diameter deviation (S) by the following formula. CV = S/Avex100 Here, S = Τ' (( Σ X — Ave) 2/n), X-ray observation 値, η-system observations. (2) Oxygen adhesion amount of the asphalt-based infusible fiber fabric The oxygen adhesion amount of the asphalt-based infusible fiber fabric was evaluated by CHNS-O Analyzer (Flash EA 1112 Series by Thermo ELECTRON CORPRATION). (3) Evaluation of d002 'Lc, La -20- 201042105 d002 and the crystallite size from the thickness direction of the octagonal mesh surface are obtained by using the ray obtained from the (002) plane, from the growth direction of the hexagonal mesh surface. The crystallite size is obtained by using a ray obtained from the (i) surface. In addition, the method of seeking a service is carried out in accordance with the Gakushin method. (4) Determination of melt viscosity 沥青 The viscosity of the asphalt passing through the capillary was determined using a capillary rheometer CAPILOGRAPH 1D (Toyo Seiki Co., Ltd.). In addition, the shear rate of the asphalt passing through the capillary is obtained by the following formula.
(a) 7 = 8 V/D (此處’ 7係毛細管內之中間相瀝青的剪切速率（s-i )、D係毛細管之孔徑（m ) 、V係毛細管內之中間相瀝 青的流速（m/s )，分別指這些意思。） 〇 另外’毛細管內之中間相瀝青的流速，係從齒輪泵所 送液的每單位時間送液量，算出通過毛細管的樹脂速度’ 而藉此求得。 另外’樹脂溫度’係以安裝在毛細管上部而且附帶熱 電偶的樹脂壓力偵測器NP463-1/2-10MPA-15/45-K (日本 Dyni sco股份有限公司製）進行監測而決定。 (5 )軟化點 軟化點係使用 METTLER FP90(Mettler Toledo 股份 -21 - 201042105 有限公司製），在氮氣環境下，由260°C開始以1°C /分鐘 昇溫而求得。 (6 )瀝青系碳纖維前驅物之配向度 在金屬紡嘴正下方，往纖維軸方向拉伸並聚集在一起 的狀態下，捕集瀝青系碳纖維前驅物之後，將試樣設置於 纖維試樣台，以廣角X射線繞射法（β掃描）進行測定。 X射線繞射裝置，係使用R i g a k u公司製4 0 3 6 A 2型；測定 結晶面角度的裝置：測角計，係採用 Rigaku公司製 2155D型，以測定範圍（β) 90〜270°，步進幅度0.5°進行 測定。配向度，係往圓周方向掃描繞射峰（β掃描），從 所得到之強度分布之半値寬度，藉由下式（b )計算。 (b)配向度=(180 — H) /180 (此處，Η意指半値寬度[deg·]) (7 )空氣風速 藉由壓克力錐形管流量計（流體工業股份有限公司製 )測定風量，將流量除以吸引槍的剖面積，藉此算出風速 (8 )瀝青系碳纖維的拉伸強度、拉伸彈性率 瀝青系碳纖維的拉伸強度、拉伸彈性率，係將1 2 0根 碳纖維絲拉緊，在測定各個纖維徑之後，對1 2 0根之機械 強度，以萬能拉力試驗機（Tensilon )測定裝置（ -22- 201042105 ORIENTEC RTC-1 150A )進行測定，求得拉伸強度、拉伸 彈性率之全數平均値而藉此決定。 (9 )由X射線繞射法進行的d002、Lc、La之評估 構成石墨的石墨層之面間隔（d002 )及來自六角網面 之厚度方向的微晶大小（Lc )，係使用由（002 )面得到 的繞射線而求得，來自六角網面之成長方向之微晶大小（ 〇 La )，係使用由（1 1 0 )面得到的繞射線而求得。另外， 求得的方法，係依據學振法來實施。 (1 〇 )瀝青系碳短纖維的纖維長測定 瀝青系碳短纖維之平均纖維長，爲數目平均纖維長， 係在光學顯微鏡下，以測長器測定2000根以上，並由其 平均値求得。倍率係因應纖維長而適宜調整。 〇 [實施例1] 將由芳香族烴所構成之中間相率1 〇〇%、軟化溫度277 °C之中間相瀝青，於3 28 °c，使用直徑 0.2mm φ 、長度 2mm、紡絲孔 41孔的金屬紡嘴，以毛細管內流速 0.185 m/s (剪切速率r : 7400s·1)送液，且在金屬紡嘴下 40cm之位置設置吸引槍，以風速740m/分鐘並與紡絲方向 平行之空氣噴流牽引熔融中間相瀝青，製作出由平均直徑 1 0.2 μπι、絲直徑C V爲4.5 %之長纖維所構成之瀝青系碳纖 維前驅物織物。以毛細管流變儀評估的328 °C、剪切速率 -23- 201042105 7 4 0 0 s _1之熔融黏度爲1 7.5 ( P a · s )。另外，由大約紡絲 筒的中間所取樣出來的瀝青系碳纖維前驅物，其配向度爲 8 5 .1 %。以上述條件牽引出的熔融中間相瀝青之間，斷絲 並未發生。另外，將本發明的紡絲裝置槪略圖揭示於圖1 。瀝青系碳纖維前驅物配向度測定所用的試樣，係藉由在 圖1之紡絲筒設置取樣處並收集試樣而取得。 接下來，在空氣環境下，以3 0分鐘，使碳纖維前驅 物織物由200°C昇溫至320°C，得到瀝青系不熔化纖維織 物。瀝青系不熔化纖維織物之氧附著量爲7.2 wt%。接著 ，在氬氣環境下，將上述瀝青系不熔化纖維織物由室溫開 始花費5小時昇溫至3 000 °C而燒成，製作出瀝青系碳纖維 織物。構成瀝青系碳纖維織物的瀝青系碳纖維之平均纖維 徑爲8.1 μπι，纖維徑之CV値爲4.7%。以X射線繞射法所 求得的 d002 爲 0.3364(nm) 、Lc 爲 44(nm) 、La 爲 116 ( nm)。另外，瀝青系碳纖維的拉伸強度爲4.5 GP a、 拉伸彈性率爲7 8 0 G P a。 [實施例2] 在氬氣環境下，使實施例1之瀝青系不熔化纖維織物 ，由室溫開始花費2小時昇溫至1 500°C而燒成，製作出瀝 青系碳纖維織物。瀝青系碳纖維的拉伸強度爲3.9GPa、拉 伸彈性率爲23 5 GPa。 [實施例3] -24- 201042105 在氮氣環境下，以800 °C將實施例1之方法所製作的 瀝青系不熔化纖維織物加以燒成’得到瀝青系碳纖維織物 ，之後進一步以渦輪硏磨機進行粉碎處理，得到粉碎物。 接著在氬氣環境下’由室溫開始花費5小時昇至3 000°C而 燒成，製作出瀝青系碳短纖維。瀝青系碳短纖維之平均纖 維徑爲8.3 μιη，纖維徑之CV値爲4.8%。另外’以X射線 繞射法所求得的d002爲0.3 365 ( nm ) 、Lc爲42 ( nm ) 、：La爲111 (nm)。另外，瀝青系碳短纖維的數目平均纖 維長爲5 5 μηι。 [實施例4] 將由芳香族烴所構成之中間相率1 〇〇%、軟化溫度276 °C之中間相瀝青，於3 3 0 °C ，使用直徑〇.2mm φ 、長度 2mm、紡絲孔 41孔的金屬紡嘴，以毛細管內流速 0.3 1 3m/s (剪切速率7 : 1 2500s·1 )送液，且在金屬紡嘴 Q 下40cm的位置設置吸引槍，以風速670m/分鐘並與紡絲 方向平行之空氣噴流牽引熔融中間相瀝青，製作出由平均 直徑14.2 μπι、絲直徑的CV爲4.5%之長纖維所構成之瀝 青系碳纖維前驅物織物。以毛細管流變儀評估的3 3 0 °C、 剪切速率12500s·1之熔融黏度，爲12.5 (Pa‘s)。另外， 由大約紡絲筒的中間所取樣出來的瀝青系碳纖維前驅物， 其配向度爲84.7%。另外，以上述條件牽引出熔融中間相 瀝青的時候，並未發生斷絲。 接下來，在空氣環境下，使碳纖維前驅物織物以30 -25- 201042105 分鐘的時間由200°C昇溫至3 3 0°C，得到瀝青系不熔化纖 維織物。瀝青系不熔化纖維織物之氧附著量爲7.1 wt%。 接著，在氬氣環境下’使上述瀝青系不熔化纖維織物由室 溫開始花費5小時昇至3 000 °C而燒成，製作出瀝青系碳纖 維織物。構成瀝青系碳纖維織物的瀝青系碳纖維之平均纖 維徑爲1 Ι.ίμιη，纖維徑之CV値爲4.2%。另外，以X射 線繞射法所求得的d002爲0.3 3 62 ( nm ) 、Lc爲52 ( nm )、1^爲146(11111)。另外，瀝青系碳纖維的拉伸強度爲 4.5GPa、拉伸彈性率爲820GPa。 [實施例5] 在氬氣環境下，使實施例4之瀝青系不熔化纖維織物 ，由室溫開始花費2小時昇溫至1 500°C而燒成，製作出瀝 青系碳纖維織物。瀝青系碳纖維的拉伸強度爲4.0GPa、拉 伸彈性率爲240GPa。 [實施例6 ] 在氮氣環境下，以800°C將實施例4之方法，將所製 作的瀝青系不熔化纖維織物加以燒成，得到瀝青系碳纖維 織物，之後進一步以渦輪硏磨機進行粉碎處理，而得到粉 碎物。接著在氬氣環境下，使其由室溫開始花費5小時昇 溫至3 000 °C而燒成，製作出瀝青系碳短纖維。瀝青系碳短 纖維之平均纖維徑爲1 1 . 3 μηι，纖維徑之C V値爲5 · 1 %。 另外，以X射線繞射法所求得的d002爲0.3 3 63 ( nm )、 -26- 201042105(a) 7 = 8 V/D (here, the shear rate of the mesophase pitch in the 7-series capillary (si), the pore size of the D-series capillary (m), and the flow rate of the mesophase pitch in the V-series capillary (m /s) means these meanings respectively.) The flow rate of the mesophase pitch in the 'capillary tube' is calculated from the amount of liquid supplied per unit time from the gear pump, and the resin velocity of the capillary tube is calculated. Further, the 'resin temperature' was determined by monitoring with a resin pressure detector NP463-1/2-10MPA-15/45-K (manufactured by Dyni Scot Co., Ltd., Japan) attached to the upper portion of the capillary and having a thermocouple. (5) Softening point The softening point was determined by using METTLER FP90 (manufactured by Mettler Toledo Co., Ltd. - 21 - 201042105) under a nitrogen atmosphere at a temperature of 1 ° C /min from 260 ° C. (6) The orientation of the pitch-based carbon fiber precursor is set directly on the fiber sample stage after the asphalt-based carbon fiber precursor is trapped in the state of being stretched and gathered in the fiber axis direction directly under the metal spout. The measurement was carried out by a wide-angle X-ray diffraction method (β scan). The X-ray diffraction device is a 4 0 3 6 A 2 type manufactured by Rigaku Co., Ltd.; a device for measuring the crystal surface angle: a goniometer, which is a 2155D type manufactured by Rigaku Co., Ltd., and has a measurement range (β) of 90 to 270°. The measurement was performed with a step width of 0.5°. The degree of alignment is obtained by scanning a diffraction peak (β scan) in the circumferential direction from the half width of the obtained intensity distribution by the following formula (b). (b) Alignment = (180 - H) / 180 (here, Η means half width [deg·]) (7) Air wind speed by acrylic cone flowmeter (manufactured by Fluid Industries, Inc.) The air volume is measured, and the flow rate is divided by the sectional area of the suction gun, thereby calculating the wind speed (8) tensile strength of the pitch-based carbon fiber, tensile modulus, tensile strength of the pitch-based carbon fiber, and tensile modulus, which are 1 2 0 The carbon fiber filaments are tensioned, and after measuring the respective fiber diameters, the mechanical strength of 120 pieces is measured by a Tensilon measuring device (-22-201042105 ORIENTEC RTC-1 150A) to obtain an elongation. The total number of strengths and tensile modulus of elasticity is determined by the average. (9) Evaluation of d002, Lc, and La by X-ray diffraction method The interplanar spacing (d002) of the graphite layer of graphite and the crystallite size (Lc) from the thickness direction of the hexagonal mesh surface are used by (002) The radii obtained from the surface were obtained, and the crystallite size (〇La) from the growth direction of the hexagonal mesh surface was obtained by using a ray obtained from the (1 1 0) plane. In addition, the method obtained is implemented in accordance with the method of learning vibration. (1 〇) Fiber length of pitch-based carbon short fibers The average fiber length of the pitch-based carbon short fibers is the number average fiber length, which is determined by an optical microscope, and more than 2000 are measured by a length measuring device, and the average is requested. Got it. The magnification is adjusted according to the length of the fiber. 〇 [Example 1] A mesophase pitch composed of an aromatic hydrocarbon having an intermediate phase ratio of 1% by weight and a softening temperature of 277 °C was used at 3 28 ° C, and a diameter of 0.2 mm φ and a length of 2 mm were used. The metal spout of the hole was fed with a flow rate of 0.185 m/s in the capillary (shear rate r: 7400 s·1), and a suction gun was set at a position of 40 cm under the metal spout at a wind speed of 740 m/min and the spinning direction. Parallel air jets were used to draw the melted mesophase pitch to produce a pitch-based carbon fiber precursor fabric composed of long fibers having an average diameter of 1 0.2 μm and a wire diameter CV of 4.5%. The melt viscosity at 328 °C, shear rate -23- 201042105 7 4 0 0 s _1, as assessed by capillary rheometer, was 1 7.5 (P a · s ). Further, the pitch-based carbon fiber precursor sampled from the middle of the spinning cylinder had an orientation of 85. 1%. Broken filaments did not occur between the molten mesophase pitches drawn under the above conditions. Further, a schematic view of the spinning apparatus of the present invention is shown in Fig. 1. The sample used for the measurement of the orientation of the pitch-based carbon fiber precursor was obtained by setting a sampling place in the spinning cylinder of Fig. 1 and collecting the sample. Next, the carbon fiber precursor fabric was heated from 200 ° C to 320 ° C in an air atmosphere for 30 minutes to obtain a pitch-based infusible fiber fabric. The asphalt-based infusible fiber fabric had an oxygen adhesion amount of 7.2 wt%. Then, the pitch-based infusible fiber fabric was heated in an argon atmosphere for 5 hours from room temperature to 3 000 ° C to be fired to produce a pitch-based carbon fiber woven fabric. The pitch-based carbon fibers constituting the pitch-based carbon fiber woven fabric had an average fiber diameter of 8.1 μm and a fiber diameter of C4.7 of 4.7%. The d002 obtained by the X-ray diffraction method is 0.3364 (nm), Lc is 44 (nm), and La is 116 (nm). Further, the pitch-based carbon fiber has a tensile strength of 4.5 GP a and a tensile modulus of 7 8 0 G P a. [Example 2] The asphalt-based infusible fiber woven fabric of Example 1 was heated in an argon atmosphere for 2 hours from room temperature to 1,500 ° C to be fired to produce a leached carbon fiber woven fabric. The pitch-based carbon fiber had a tensile strength of 3.9 GPa and a tensile modulus of 23 5 GPa. [Example 3] -24- 201042105 The pitch-based infusible fiber fabric produced by the method of Example 1 was fired at 800 ° C in a nitrogen atmosphere to obtain a pitch-based carbon fiber fabric, followed by a turbine honing machine. The pulverization treatment was carried out to obtain a pulverized product. Then, it was fired in an argon atmosphere for 5 hours from room temperature to 3 000 ° C to produce pitch-based carbon short fibers. The average carbon fiber diameter of the pitch-based carbon short fibers was 8.3 μηη, and the fiber diameter CV値 was 4.8%. In addition, the d002 obtained by the X-ray diffraction method is 0.3 365 (nm), Lc is 42 (nm), and La is 111 (nm). Further, the number of pitch-based carbon short fibers has an average fiber length of 5 5 μη. [Example 4] A mesophase pitch composed of an aromatic hydrocarbon having an intermediate phase ratio of 1% by weight and a softening temperature of 276 °C was used at 340 ° C, and a diameter of 〇.2 mm φ and a length of 2 mm were used. The 41-hole metal spun nozzle was supplied with a flow rate of 0.3 1 3 m/s (shear rate 7 : 1 2500 s·1 ) in the capillary tube, and a suction gun was set at a position of 40 cm under the metal spout Q at a wind speed of 670 m/min. The air jet parallel to the spinning direction draws the molten mesophase pitch to produce a pitch-based carbon fiber precursor fabric composed of long fibers having an average diameter of 14.2 μm and a wire diameter of CV of 4.5%. The melt viscosity at a temperature of 3 30 ° C and a shear rate of 12500 s·1 as measured by a capillary rheometer was 12.5 (Pa's). Further, the pitch-based carbon fiber precursor sampled from the middle of the spinning cylinder had an alignment degree of 84.7%. Further, when the molten mesophase pitch was pulled out under the above conditions, no broken yarn occurred. Next, the carbon fiber precursor fabric was heated from 200 ° C to 340 ° C in an air atmosphere for 30 - 25 - 201042105 minutes to obtain a pitch-based infusible fiber fabric. The asphalt-based infusible fiber fabric had an oxygen adhesion amount of 7.1 wt%. Then, the above-mentioned pitch-based infusible fiber woven fabric was heated in an argon atmosphere from the room temperature for 5 hours to 3 000 ° C to be fired to produce a pitch-based carbon fiber woven fabric. The pitch-based carbon fibers constituting the pitch-based carbon fiber woven fabric have an average fiber diameter of 1 Ι. ίμιη, and the fiber diameter CV 値 is 4.2%. Further, the d002 obtained by the X-ray diffraction method was 0.3 3 62 (nm), Lc was 52 (nm), and 1^ was 146 (11111). Further, the pitch-based carbon fiber had a tensile strength of 4.5 GPa and a tensile modulus of 820 GPa. [Example 5] The asphalt-based infusible fiber woven fabric of Example 4 was heated in an argon atmosphere for 2 hours from room temperature to 1,500 ° C to be fired to produce a leached carbon fiber woven fabric. The pitch-based carbon fiber had a tensile strength of 4.0 GPa and a tensile modulus of 240 GPa. [Example 6] The obtained pitch-based infusible fiber fabric was fired at 800 ° C in a nitrogen atmosphere at 800 ° C to obtain a pitch-based carbon fiber fabric, which was further pulverized by a turbine honing machine. Treated to obtain a pulverized material. Then, it was baked in an argon atmosphere for 5 hours from room temperature to 3 000 ° C to produce pitch-based carbon short fibers. The average fiber diameter of the pitch-based carbon short fibers was 11.1 μm, and the fiber diameter C V値 was 5.1 %. In addition, the d002 obtained by the X-ray diffraction method is 0.3 3 63 ( nm ), -26- 201042105
Lc爲48(nm) 、La爲137 (nm)。另外，瀝青系碳短纖 維的數目平均纖維長爲230μιη。 [比較例1] 將由芳香族烴所構成之中間相率1 〇〇%、軟化溫度276 t：之中間相瀝青，於3 3 8 °C，使用由直徑〇_2mm φ、長度 2mm之正圓形紡絲孔所構成之金屬防嘴，以毛細管內流速 0 0.223m/s (剪切速率r : 8920s·1 )送液，且由紡絲孔旁邊 的狹縫，以相對於纖維軸呈35度角、每分鐘1 0800m，吹 送343 °C的空氣，牽引出熔融中間相瀝青，製作出平均直 徑15.3 μηι之碳纖維前驅物織物。另外，以毛細管流變儀 評估的3 3 8 °C、剪切速率8920s·1之熔融黏度爲8.2(Pa*s )。以上述條件將熔融中間相瀝青紡絲的時候，觀察到斷 絲明顯地發生。另外，在金屬紡嘴正下方所捕集到的瀝青 系碳纖維前驅物，其配向度爲83.2%。接下來在空氣環境 〇 下以3 0分鐘的時間，使由碳纖維前驅物所構成之織物由 2 00°C昇溫至320°C，得到不熔化碳纖維所構成之織物。不 熔化碳纖維之氧附著量爲7.6wt%。接著，在氬氣環境下 ’將上述瀝青系不熔化纖維所構成之織物，由室溫開始花 費5小時昇溫至3 000 °C而燒成，製作出由瀝青系碳纖維所 構成之織物。瀝青系碳纖維之平均纖維徑爲10.3μιη，纖 維徑之CV値爲10.8%。另外，瀝青系碳纖維的拉伸強度 爲2.2GPa、拉伸彈性率爲740GPa。將比較例1之紡絲裝 置之槪略圖揭示於圖2。 -27- 201042105 [比較例2] 在氬氣環境下，使比較例1之瀝青系不熔化纖維織物 ，由室溫開始花費2小時昇溫至1 500°c而燒成’製作出瀝 青系碳纖維織物。瀝青系碳纖維的拉伸強度爲1.6GPa、拉 伸彈性率爲225GPa。 [比較例3 ] ft 將由芳香族烴所構成之中間相率1 〇〇%、軟化溫度276 °C之中間相瀝青，於3 3 8 °C ，使用直徑0.2mm φ 、長度 2mm、紡絲孔 41孔的金屬紡嘴，以毛細管內流速 0.223 m/s (剪切速率r : 8920s·1)送液，且在金屬紡嘴下 4 0cm的位置設置吸引槍，打算以風速670m/分鐘並與紡絲 方向平行之空氣噴流牽引熔融中間相瀝青，然而斷絲卻頻 繁地發生。另外，以毛細管流變儀評估的3 3 8 t、剪切速 率8920s·1之熔融黏度爲6.2 ( Pa .S )。構成碳纖維前驅物 lj 織物之碳纖維前驅物之絲直徑之C V値爲3 2 %。 【圖式簡單說明】 圖1係實施例1及3之紡絲裝置之槪略圖 圖2係比較例1之紡絲裝置之槪略圖 【主要元件符號說明】 1 :金屬紡嘴 -28- 201042105 2 :吸引槍 3 :碳纖維前驅物 4 :紡絲筒 5 :捕集機 6 :風的流向 7 :碳纖維前驅物織物 8 :吸引機 9 :取樣口 1 〇 :流量計 1 1 :空氣噴出部 1 2 :金屬紡嘴 1 3 :紡絲筒 1 4 :捕集機 1 5 :碳纖維前驅物織物 1 6 :碳纖維前驅物Lc is 48 (nm) and La is 137 (nm). Further, the number average pitch of the pitch-based carbon short fibers was 230 μm. [Comparative Example 1] A mesophase pitch composed of an aromatic hydrocarbon having an intermediate phase ratio of 1% by weight and a softening temperature of 276 t: at a temperature of 3 3 8 ° C, a perfect circle having a diameter of 〇 2 mm φ and a length of 2 mm was used. The metal anti-nozzle formed by the spinning hole is fed with a flow rate of 0 0.223 m/s (shear rate r: 8920 s·1) in the capillary tube, and is formed by a slit beside the spinning hole to be 35 with respect to the fiber axis. At a degree angle of 1,0800 m per minute, air of 343 ° C was blown, and the molten mesophase pitch was pulled out to produce a carbon fiber precursor fabric having an average diameter of 15.3 μηι. In addition, the melt viscosity at 3 3 8 ° C and the shear rate of 8920 s·1 evaluated by a capillary rheometer was 8.2 (Pa*s ). When the molten mesophase pitch was spun under the above conditions, it was observed that the broken yarn occurred remarkably. Further, the pitch-based carbon fiber precursor trapped directly under the metal spun nozzle had an alignment degree of 83.2%. Next, the fabric composed of the carbon fiber precursor was heated from 200 ° C to 320 ° C in an air atmosphere for 30 minutes to obtain a fabric composed of infusible carbon fibers. The oxygen-adhering amount of the non-melting carbon fiber was 7.6 wt%. Then, the woven fabric composed of the above-mentioned pitch-based infusible fibers was heated in an argon atmosphere for 5 hours from room temperature to 3 000 ° C to be fired, thereby producing a woven fabric composed of pitch-based carbon fibers. The average fiber diameter of the pitch-based carbon fiber was 10.3 μm, and the fiber diameter CV値 was 10.8%. Further, the pitch-based carbon fiber had a tensile strength of 2.2 GPa and a tensile modulus of 740 GPa. A schematic view of the spinning apparatus of Comparative Example 1 is shown in Fig. 2. -27- 201042105 [Comparative Example 2] In the argon atmosphere, the pitch-based infusible fiber fabric of Comparative Example 1 was heated from room temperature to 1500 ° C for 2 hours to be fired to produce a pitch-based carbon fiber fabric. . The pitch-based carbon fiber had a tensile strength of 1.6 GPa and a tensile modulus of 225 GPa. [Comparative Example 3] ft A mesophase pitch composed of an aromatic hydrocarbon having an intermediate phase ratio of 1% by weight and a softening temperature of 276 °C, at a temperature of 3 3 8 ° C, using a diameter of 0.2 mm φ and a length of 2 mm, a spinning hole The 41-hole metal spun nozzle was supplied with a flow rate of 0.223 m/s (shear rate r: 8920 s·1) in the capillary, and a suction gun was placed at a position of 40 cm under the metal spout. It was intended to wind at 670 m/min and Air jets that are parallel in the direction of spinning draw the molten mesophase pitch, but broken wires occur frequently. In addition, the melt viscosity of 3 3 8 t and shear rate 8920 s·1 evaluated by a capillary rheometer was 6.2 (Pa .S ). The carbon diameter of the carbon fiber precursor constituting the carbon fiber precursor lj fabric has a C V 3 of 32%. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a spinning apparatus of Embodiments 1 and 3; Fig. 2 is a schematic view of a spinning apparatus of Comparative Example 1 [Description of main components] 1 : Metal spun -28- 201042105 2 : suction gun 3 : carbon fiber precursor 4 : spinning drum 5 : trap 6 : flow direction of wind 7 : carbon fiber precursor fabric 8 : suction machine 9 : sampling port 1 〇 : flow meter 1 1 : air ejection portion 1 2 : Metal Spinner 1 3 : Spinning Cartridge 1 4 : Collector 1 5 : Carbon Fiber Precursor Fabric 1 6 : Carbon Fiber Precursor