201009146 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有高延伸度及彈性率之含有瀝青系碳 纖維之不織布’由該等構成之毛氈、隔熱材以及該等之製 造方法。更詳細而言，係關於含有以中間相瀝青作爲原料 在特定條件下不融化，經燒成之瀝青系碳纖維之不織布， 由該等構成之耐久性、耐氧化性優異之毛氈與隔熱材。 參 【先前技術】 以聚丙烯腈爲原料之碳纖維爲具有均衡之摘取強度與 彈性率，且已廣泛使用作爲產業用機械臂或飛機之構造構 件。爲了達成將碳纖維作爲汽車用構件等進一步之擴大用 途’有必要降低成本。然而，以聚丙烯腈爲原料之碳纖維 之起始原料爲合成樹脂，在降低成本上受到限制。 至於低成本碳纖維有以石油或煤碳殘留物之瀝青作爲 ® 原料之瀝青系碳纖維。瀝青系碳纖維大致上分爲以等向性 瀝青作爲原料之碳纖維及與以中間相瀝青作爲原料之碳纖 維。 以等向性瀝青作爲原料之瀝青系碳纖維有如同例如專 利文獻1中所述之延伸度超過2%之高延伸度碳纖維。然 而，一方面，具有石墨化性低而無法獲得高彈性率碳纖維 之缺點。另一方面，以中間相瀝青作爲原料之碳纖維由於 其優異之石墨化性而可輕易地達成高彈性率。然而，由於 以高溫燒成之石墨結晶發達，儘管可達成高彈性率化，但 -5- 201009146 延伸度降低，結果有強度變低之缺點。據此，製造具有高 延伸度及高彈性率之瀝青系碳纖維極爲困難。 至於解決該問題之手段，已提出將原料瀝青改質之方 法。例如專利文獻2提出在氟化氫及三氟化硼存在下使縮 合多環烴在100~400°C下聚合，獲得光學各向異性含量未 達5%之瀝青後，進一步在250〜450°C下熱聚合獲得之氫對 於碳之原子比在0.5〜0.7、全芳香族碳中配向碳量爲50% 以下、5~150μιη之各向異性球體爲5〜60%、吡啶不溶成份 ❹ 爲25重量％以下之原料。然而，該方法由於觸媒係使用氟 化氫及三氟化硼等強酸，因此需要使用特殊設備，且有反 應後萃取之廢酸之處理需要花費巨大費用之問題。 另外專利文獻3中提出在中間相瀝青中使交聯化劑反 應，利用所得反應物做爲原料之碳纖維製造方法。但，該 方法中由於亦使用特殊之交聯化劑，因此亦具有成本高等 問題。 至於提高瀝青系碳纖維強度之其他方法，專利文獻4 Q 中揭示在瀝青纖維中於不含氧之下含有碘’接著在惰性氛 圍下經熱處理製造瀝青系碳纖維之方法。但’該方法須使 碳化步驟中吸附於瀝青上之碘脫離’其結果有使爐之壽命 顯著降低等之缺點。 又專利文獻5中提出使以紡絲獲得之碳纖維前驅物不 融化，使產生之瀝青系不融化纖維在惰性氛圍中’於 700 t：以下施加張力，在繃緊之下進行熱處理’接著在惰 性氛圍中使不融化之纖維在未繃緊之下碳化及石墨化之方 -6- 201009146 法。然而該方法雖有可能碳纖維前驅物係長纖維之情況’ 但會有例如爲了使以熔融吹製法製備之碳纖維前驅物成爲 不織布狀而無法採用之問題。[Technical Field] The present invention relates to a felt comprising a pitch-based carbon fiber having a high elongation and an elastic modulus, a felt comprising the material, a heat insulating material, and a manufacturing method therefor. More specifically, the present invention relates to a felt and a heat insulating material which are excellent in durability and oxidation resistance which are composed of a non-woven fabric of a pitch-based carbon fiber which is not melted under specific conditions and which is not melted under specific conditions. [Prior Art] Carbon fiber using polyacrylonitrile as a raw material has a balanced extraction strength and elastic modulus, and has been widely used as a structural member of an industrial robot arm or an aircraft. In order to achieve further expansion of carbon fiber as a component for automobiles, it is necessary to reduce costs. However, the starting material of the carbon fiber using polyacrylonitrile as a raw material is a synthetic resin, which is limited in cost reduction. As for low-cost carbon fibers, there are pitch-based carbon fibers with petroleum or coal-carbon residue as the raw material. The pitch-based carbon fiber is roughly classified into a carbon fiber using an isotropic pitch as a raw material and a carbon fiber using a mesophase pitch as a raw material. The pitch-based carbon fiber using the isotropic pitch as a raw material has a high elongation carbon fiber having an elongation of more than 2% as described in, for example, Patent Document 1. On the one hand, however, it has the disadvantage that the graphitization is low and the high modulus carbon fiber cannot be obtained. On the other hand, a carbon fiber using mesophase pitch as a raw material can easily achieve a high modulus of elasticity due to its excellent graphitization property. However, since graphite crystals which are fired at a high temperature are developed, although high modulus of elasticity can be achieved, the elongation of -5 to 201009146 is lowered, and as a result, the strength is lowered. Accordingly, it is extremely difficult to produce pitch-based carbon fibers having high elongation and high modulus of elasticity. As a means of solving this problem, a method of modifying raw material pitch has been proposed. For example, Patent Document 2 proposes to polymerize a condensed polycyclic hydrocarbon at 100 to 400 ° C in the presence of hydrogen fluoride and boron trifluoride to obtain an asphalt having an optical anisotropy content of less than 5%, and further at 250 to 450 ° C. The atomic ratio of hydrogen obtained by thermal polymerization to carbon is 0.5 to 0.7, the amount of aligned carbon in the wholly aromatic carbon is 50% or less, the anisotropic sphere of 5 to 150 μm is 5 to 60%, and the pyridine insoluble component ❹ is 25% by weight. The following raw materials. However, this method uses a strong acid such as hydrogen fluoride or boron trifluoride because of the catalyst, so that special equipment is required, and the treatment of the spent acid extracted after the reaction requires a large cost. Further, Patent Document 3 proposes a carbon fiber production method in which a cross-linking agent is reacted in mesophase pitch and a obtained reactant is used as a raw material. However, since this method also uses a special crosslinking agent, it also has a high cost problem. As another method for increasing the strength of the pitch-based carbon fiber, Patent Document 4 Q discloses a method of producing pitch-based carbon fibers by heat-treating in an asphalt fiber without oxygen under an inert atmosphere. However, this method requires the iodine adsorbed on the asphalt in the carbonization step to be detached, and as a result, there is a disadvantage that the life of the furnace is remarkably lowered. Further, in Patent Document 5, it is proposed that the carbon fiber precursor obtained by spinning is not melted, and the produced pitch-based non-melting fiber is subjected to heat treatment in an inert atmosphere at a pressure of 700 t: or less, followed by heat treatment under tension. In the atmosphere, the unmelted fiber is carbonized and graphitized without being tightened. -6-201009146. However, this method may be a case where the carbon fiber precursor is a long fiber, but there is a problem that it cannot be used, for example, in order to make the carbon fiber precursor prepared by the melt blowing method into a non-woven fabric.
又專利文獻6介紹在含有0.1〜40容量％之Ν02及 4〜40容量％之Η20之氧化性氛圍下，於100〜400°C之溫度 範圍內進行不融化處理而製造強度獲改善之碳纖維之製造 方法。但該方法如實施例中所示成爲有關彈性率降低者。 如上述般，製造具有高延伸度及高彈性率之瀝青系碳 纖維極爲困難。 (專利文獻1 ) (專利文獻2 ) (專利文獻3) (專利文獻4 ) (專利文獻5) (專利文獻6) 特開平2- 1 69727號公報 特開平9-279 1 54號公報 特開平1-207420號公報 特開平8-27628號公報 特開招62-69826號公報 特開平2-6618號公報 Φ 【發明內容】 如此，以中間相瀝青作爲原料之碳纖維爲具有優異彈 性率，相反地，相較於以等向性瀝青作爲原料之碳纖維， 其拉伸延伸度低，有在例如作爲產業用機械臂或飛機之構 造構件用途難以開展之問題點。 因此，本發明之目的係提供一種提高源自中間相瀝青 之碳纖維缺點之拉伸延伸度，且過去所沒有之高延伸度及 高彈性率之含有瀝青系碳纖維之不織布。又本發明之目的 201009146 係提供一種對具高延伸度及彈性率之含有瀝青系碳纖維之 不織布進行針扎（needle punch)處理之毛氈，以及由該 等構成之隔熱材。 本發明者發現在以中間相瀝青作爲原料之碳纖維製造 步驟中之不融化處理中，製造氧加成量爲8〜15重量％之不 融化纖維，且在800〜1，800°C下燒成可獲得拉伸延伸度獲 得改善，具有過去不具有之高延伸度，且具有高彈性率之 含有瀝青系碳纖維之不織布而完成本發明。 亦即，本發明包含以下之發明。 1. 一種不織布，其爲含有瀝青系碳纖維之不織布， 其特徵爲該瀝青系碳纖維爲： (i)以光學顯微鏡觀測之平均纖維徑（D1)大於 2μιη且爲20μιη以下， (Π)相對於以光學顯微鏡觀測之平均纖維徑（D1) 之纖維徑分散（S1)之100分率爲3〜20 %， (iii )拉伸彈性率爲80〜300GPa，及 (iv)拉伸延伸度爲1.4〜2.5%。 2. 如上述1所述之不織布，其中瀝青系碳纖維之拉 伸彈性率爲100~300GPa，拉伸延伸度爲1.5-2.4%。 3. 如上述1所述之不織布，其中以光學顯微鏡觀測 瀝青系碳纖維之平均纖維徑（D1)大於ΙΟμιη且爲20μίη 以下。 4.如上述 1所述之不織布，其中拉伸強度爲 1 0N/5cm片以上。 201009146 5. —種不織布之製造方法，該方法包含下列各步驟 (1) 將中間相瀝青進行紡絲，製造含有碳纖維前驅 物之前驅物織物， (2) 在氧化性氣體氛圍下中不使前驅物織物融化， 製造含有氧加成量8〜15重量％之碳纖維之不融化織物，及 (3) 使不融化織物在800〜1，800 °C下燒成。 0 6.如上述5所述之製造方法，其中紡絲係以熔融吹 製法進行。 7·如上述5所述之製造方法，其中前驅物織物之碳 纖維前驅物之平均纖維長度爲4〜25 cm。 8.如上述5所述之製造方法，其中不融化織物之碳 纖維之氧加成量爲9〜12重量％。 9·如上述5所述之製造方法，其中燒成前後之以下 式（I)表示之纖維長度維持率（％ )爲90 %以上， φ 纖維長度維持率=100x1^/1^° ⑴ L、燒成前之纖維長度 L1:燒成後之纖維長度。 10. —種毛氈’其特徵係藉由使上述1所述之不織布 經針扎（n e e d 1 e p u n c h )處理所獲得。 1 1 .如上述1 〇所述之毛β，其厚度方向之層間剝離 強度爲〇.25N/5cm片以上。 12.如上述10所述之毛耗，其中碳纖維之平均纖維 徑爲大於ΙΟμιη且爲20μιη以下’且單位面積重量爲25〇~ 201009146 1,000g/m2 0 13. —種石墨化毛氈，其係藉由使上述i〇所述之毛 耗進一步在2,000〜3,500°C下經熱處理而獲得。 14. 一種毛氈之製造方法，其特徵爲包含下列各步驟 (1) 將中間相瀝青進行紡絲，製造含有碳纖維前驅 物之前驅物織物， (2) 在氧化性氣體氛圍中不使前驅物織物融化，製 參 造含有氧加成量8〜15重量％之碳纖維之不融化織物， (3) 使不融化織物在800-1,800 t下燒成，及 (4) 使不織布進行針扎。 15. 如上述14所述之製造方法，其中不織布係以繭 絲（bave)深度爲0.15mm以上之針，以15~100次/cm2之 刺扎數進行針扎。 16. —種複合體’其特徵爲於上述1〇所述之毛氈中 含浸樹脂而得。 @ 17. —種複合體’其特徵爲於上述13所述之石墨化 毛氈中含浸樹脂而得。 18. —種隔熱材，其特徵爲將上述16所述之複合體 在500~2,200°C下熱處理而得。 19. 一種隔熱材之製造方法，其特徵爲包含下列各步 驟： (1)將上述10所述之毛氈含浸於樹脂中製造複合體 :及 -10- 201009146 (2)將複合體在500~2,200。〇進行熱處理。 【實施方式】 [不織布] 本發明爲包含瀝青系碳纖維之不織布。構成不織布之 瀝青系碳纖維之特徵爲： (i) 以光學顯微鏡觀測之平均纖維徑（D1)大於 2μιη且爲20μιη以下， (ii) 相對於以光學顯微鏡觀測之平均纖維徑（D1) 之纖維徑分散（S1)之100分率爲3〜20 %， (iii) 拉伸彈性率爲80〜300GPa，及 (iv) 拉伸延伸度爲1.4〜2.5%。 (碳纖維：拉伸彈性率及拉伸延伸度） 碳纖維會因其燒成溫度使機械特性大幅變化。據此， ❹ 拉伸彈性率及拉伸延伸度會因碳纖維製造過程中之熱經歷 而大幅變化。例如以等向性瀝青作爲原料之碳纖維在自低 溫至高溫之廣泛溫度領域下可充分達成超過1.4%之延伸 度。然而，其彈性率難以超過50 GP a。另一方面，以中間 相瀝青作爲原料之碳纖維在燒成溫度超過800°C以上時， 彈性率可超過80GP a。然而，過去之製造方法之延伸度均 小於1.4%。又，當燒成溫度未達800°C時無法達成80GPa 之彈性率。該等過去之技術難以獲得拉伸彈性率在 80〜300GPa，且拉伸延伸度在1.4〜2.5 %之範圍內之瀝青系 -11 - 201009146 碳纖維。 本發明之特徵爲在以中間相瀝青作爲原料之瀝青系碳 纖維之製造步驟中之不融化處理中’藉由製造氧加成量在 8~15重量％之不融化纖維，且使不融化纖維在800〜1，800 °C下燒成，可製造具有過去無法達到之高拉伸延伸度’且 具有高彈性率之瀝青系碳纖維。 構成本發明之不織布之瀝青系碳纖維之拉伸彈性率爲 80〜300GPa，較好爲 100〜300GP这，更好爲 180〜300GPa。 構成本發明之不織布之瀝青系碳纖維之拉伸延伸度爲 1.4〜2.5%，較好爲1.5-2.4%，更好爲1.6〜2.3%。因此構成 本發明不織布之瀝青系碳纖維較好拉伸彈性率爲1 〇〇〜 300GPa，拉伸延伸度爲1·5~2·4%，更好拉伸彈性率爲 180~300GPa，拉伸延伸度爲 1.6~2.3 %。 (碳纖維：平均纖維徑（D1)及纖維徑分散（S1)) 構成本發明之不織布之瀝青系碳纖維由於拉伸彈性率 及拉伸延伸度在上述範圍內，因而具有特定之平均纖維徑 (D1)及相對於平均纖維徑（D1)之纖維徑分散度（S1 )之100分率。 以光學顯微鏡觀測構成本發明不織布之瀝青系碳纖維 之平均纖維徑（D1)爲大於2μπι且爲20μιη以下。平均纖 維徑大於ΙΟμιη且爲20μιη以下時，成爲耐氧化性或強度 優異者而較佳。更好爲大於ΙΟμηι且爲15μιη以下。 相對於以光學顯微鏡觀測構成本發明不織布之瀝青系 -12- 201009146 碳纖維之平均纖維徑（D1)之纖維徑分散（S1)之100分 率爲3〜20%，較好爲5〜15%，更好爲8〜13%。 (不織布之拉伸強度） 本發明之不織布之拉伸強度較好爲10N/5cm片以上， 更好爲12N/5cm片以上。織布之拉伸強度爲i〇N/5cm片 以上時，可提高以針扎等之成型處理獲得之毛氈之拉伸強 φ 度。該毛氈可被用於隔熱材 '隔音材等之用途中。不織布 之拉伸強度爲以Tensilon測定裝置，將寬度5cmx長度 20cm之樣品以長度方向拉伸之値。 [不織布之製造方法] 本發明之不織布可以下列之各步驟製造： (1)將中間相瀝青進行紡絲，製造含有碳纖維前驅 物之前驅物織物[步驟（1)]， φ (2)在氧化性氣體氛圍中不使前驅物織物融化，製 造含有氧加成量8〜15重量％之碳纖維之不融化織物[步驟 (2)]，及 (3 )使不融化織物在800〜1，800。(：下燒成[步驟（3 ) j 〇 藉由該方法可獲得具有高延伸度及高彈性率之含有瀝 青系碳纖維之本發明不織布。 以下，針對本發明之各步驟依序進行說明。 -13- 201009146 (步驟（1 ):紡絲） 瀝青系碳纖維之原料較好爲中間相瀝青。中間相瀝青 之中間相率較好爲90%以上，更好爲95%以上，又更好爲 99%以上。而且，中間相瀝青之中間相率可以偏光顯微鏡 觀察熔融狀態之瀝青予以確認。中間相瀝青之原料舉例爲 例如如萘或菲之縮合多環烴化合物，如石油系瀝青或煤碳 系瀝青之縮合雜環化合物等。其中以萘或菲之縮合多環烴 化合物較佳。 n 另外，原料瀝青之軟化點較好爲2 3 0 °c以上3 4 0 °c以 下。碳纖維前驅物之不融化處理有必要在比軟化點低之溫 度下處理。據此’當軟化點低於2 3 0 °C時，有必要至少在 未達軟化點之低溫度下進行不融化處理，結果是不融化需 要長時間而不適當。另一方面，當軟化點超過340 °C時， 容易引起瀝青熱分解’而有發生之氣體在絲中產生氣泡等 之問題產生而不佳。更好之軟化點範圍爲2 5 0 °C以上3 2 0 °C以下’又更好爲260°C以上3 10°C以下。而且，原料瀝 @ 青之軟化點可以美特拉（Mettler )法求得。原料瀝青亦可 適當的組合兩種以上使用。組合之原料瀝青之中間相率至 少爲9 0 %以上’軟化點較好爲2 3 0 °C以上3 4 0。(：以下。 步驟（1 )係將中間相瀝青紡絲，製造含有碳纖維前 驅物之前驅物織物之步驟。紡絲方法並無特別限制，可槪 述提出所謂的熔融紡絲法。具體而言，舉例爲以絡紗機捲 取自模嘴吐出之中間相瀝青之一般紡絲延伸法，使用熱風 作爲噴霧源之熔融吹製法，利用離心力捲取中間相瀝青之 -14- 201009146 離心紡絲法等。其中就控制碳纖維前驅物之型態、提高生 產性等理由，以使用熔融吹製法較佳。 以下，就熔融吹製法加以描述。本發明中形成碳纖維 前驅物之紡絲噴嘴之形狀爲任何者均可。通常使用真圓狀 者，但使用適當之橢圓等異型形狀之噴嘴也無妨。噴嘴孔 之長度（LN )與孔徑（DN )之比（LN/DN )以2〜20之範 圍較佳。當LN/DN超過20時，會對通過噴嘴之中間相瀝 φ 青施加強的剪切力，使纖維剖面呈現輻射狀構造。輻射狀 構造之呈現在燒成過程中有使纖維之剖面產生破裂，造成 機械特性降低而不適當。另一方面，當LN/DN未達2時 ，無法對原料瀝青賦予剪切，結果成爲配向性低之碳纖維 。因此’即使燒成亦無法製造出優異機械特性而不適當。 爲了實現優異之機械特性，須對中間相瀝青施加適度 之剪斷力。據此’噴嘴孔之長度（LN)與孔徑（DN)之 比（LN/DN )以2〜20之範圍較佳，最好爲3〜12之範圍。 φ 紡絲時之噴嘴溫度、中間相瀝青通過噴嘴時之剪切速度、 自噴嘴吹出之風量、風的溫度等並無特別限制，只要可維 持穩定之紡絲狀態之條件，亦即中間相瀝青於噴嘴孔之熔 融黏度在1〜100 Pa. s之範圍即可。 通過噴嘴之中間相瀝青之熔融黏度未達IPa. s時， 熔融黏度過低無法維持絲形狀而不適當。另一方面，當中 間相瀝青之熔融黏度超過l〇〇Pa. s時，會對中間相瀝青 施加強的剪切力’而在纖維剖面形成輻射狀構造而不適當 。爲了使施加於中間相瀝青之剪切力在適當範圍內，且維 -15- 201009146 持纖維形狀，因此需要控制通過噴嘴之中間相瀝青之熔融 黏度。因此，較好使中間相瀝青之熔融黏度較好在1〜 lOOPa. s之範圍，更好爲3〜30Pa. s之範圍’且最好爲 5〜25Pa . s之範圍。 本發明中構成不織布之碳纖維之特徵爲平均纖維徑（ D1)大於2μιη且20μιη以下。碳纖維平均纖維徑之控制可 藉改變噴嘴之孔徑，或改變原料瀝青自噴嘴之吐出量’或 改變拉伸比而調整。拉伸比之變高可藉由將加溫至 @ 100~4()0°(：下每分鐘100〜20,000111線速度之氣體吹送至細 化點附近而達成。吹送之氣體並無特別限制，但就成本效 益與安全性之方面而言，以空氣較適當。 碳纖維前驅物被捕集至金屬網等之輸送帶上而成前驅 物織物。此時，藉由輸送帶之輸送速度可調整成任意之基 重量，但亦可依據需要藉由交叉捲棉等方法層合。前驅物 織物之基重量考慮生產性及步驟安定性，以 150~ 1，000g/m2 較佳。 @ 碳纖維前驅物之平均纖維長度以4〜25cm之範圍較佳 。當碳纖維前驅物之平均纖維長度未達4cm時，捕集於金 屬網等輸送帶上之前驅物織物之強度明顯降低，難以藉由 加交叉捲棉等方法層合，造成生產性下降故而不適當。另 一方面，當超過25cm時，前驅物織物極爲蓬鬆，於後續 步驟之不融化中，因前驅物織物與氧化性氣體反應產生之 反應熱難以去除，視情況有燒掉等問題故而不適當。碳纖 維前驅物之平均纖維長度之較佳範圍爲5~10cm。 -16- 201009146 紡絲所得之碳纖維前驅物之平均纖維徑較好大於2 μιη 且20μηι以下。當平均纖維徑爲2μπι以下時，自碳纖維前 驅物製造氧加成量爲8〜15重量％之不融化纖維之步驟中難 以控制氧加成量。因此，只因爲無法使燒成所得之碳纖維 品質穩定，視情況因不融化反應熱使碳纖維前驅物燒掉故 而不佳。另一方面，當平均纖維徑超過2 0 μπι時，自碳纖 維前驅物製造氧加成量爲8〜15重量％之不融化纖維之步驟 φ 中，製造氧加成量超過8重量％之不融化纖維時需要更多 時間，導致生產性顯著下降而不佳。碳纖維前驅物之平均 纖維徑更佳之範圍爲大於ΙΟμιη且爲20μιη以下，更好爲 大於ΙΟμιη且爲15μιη以下。 又相對於碳纖維前驅物之平均纖維徑之纖維徑分散（ S1 )之100分率以在3~20%之範圍較佳。CV値爲纖維徑 之分散之指標，於小的情況步驟安定性高，意指分散較小 。但，製作實質CV値小於3%之物件之情況，需要極力控 0 制自紡絲模嘴之各毛細管吐出之樹脂量之斑點。因此，將 紡絲模嘴變小，結果是因毛細管數降低而造成顯著之生產 性下降。另一方面，CV値大於20%之情況下，自碳纖維 前驅物製造氧加成量在7~ 15重量％之不融化纖維之步驟中 ，難以控制氧加成量，結果燒成所得之瀝青系碳纖維之品 質無法穩定而不佳。CV値更好之範圍爲8〜15 %。 (步驟（2 ):不融化） 步驟（2)爲使前驅物織物在氧化性氣體氛圍下不融 -17- 201009146 化，製造含有氧加成量爲8-15重量％之碳纖維之不融化織 物之步驟。 本發明之特徵爲步驟（2)中所得之不融化纖維之氧 加成量爲8~ 15重量％。當不融化纖維之氧加成量未達8重 量％時，於步驟（3 )中燒成所得之碳纖維之拉伸延伸度無 法超過1.4%。另一方面，當氧加成量超過15重量％時， 會引起以中間相瀝青作爲原料之瀝青系碳纖維之特徵之優 異彈性率顯著降低而不佳。爲獲得優異之拉伸延伸度及彈 @ 性率之較佳氧加成量之範圍爲8〜13重量％，尤其以9~12 重量％最佳。 碳纖維前驅物之不融化係在氧化性氣體氛圍中實施， 本發明中所謂之氧化性氣體係指空氣、或指可自碳纖維前 驅物拉取電子之氣體與空氣之混合氣體。可自碳纖維前驅 物拉取電子之氣體可例示爲臭氧、碘、溴、氧等。然而， 考慮到安全性、便利性、成本效益時，在空氣中進行碳纖 維前驅物之不融化最適當。 @ 碳纖維前驅物之不融化可爲批式處理、連續處理之任 一種處理，但考量生產性時以連續處理較佳。不融化溫度 較好爲 15〇〜35〇°C，更好爲 160〜34〇°C。瀝青處理中宜使 用之升溫速度爲1〜10 °C/分鐘。升溫速度之較佳範圍，考 慮到生產性及步驟之安定性，爲3~9°C /分鐘。連續處理之 情況下，依序通過設定在任意溫度之複數個反應室可達成 升溫速度。使碳纖維前驅物依序通過複數個反應室時，亦 可使用輸送帶等。不融化纖維之氧加成量與爐內溫度及爐 -18- 201009146 內滯留時間大有關聯。連續處理中，控制輸送帶 各反應室之溫度，且控制各反應室之滯留時間’ 系不融化絲之氧加成量成爲8〜1 5重量％而較佳。 速度亦與反應室之數目大幅相關，但較好爲〇· 鐘。 (步驟（3 ):燒成） φ 步驟（3 )爲使不融化織物在800〜1，800 °C下 不織布之步驟。 不融化織物爲在真空中，或使用氮氣、氬氣 性氣體之非氧化性氛圍中燒成而成不織布。燒成 成本面以在常壓及氮氣氛圍中處理較佳。又，可 理、連續處理之任一種處理，但若考量生產性則 理較適宜。 本發明方法中之步驟（2)之不融化纖維之 參 在8〜15重量％時，燒成步驟中以下述式（I )表 長度維持率（％ )可在90%以上。 纖維長度維持率=100x1^/1^° (I) 燒成前之纖維長度 L1:燒成後之纖維長度 纖維長度維持率之更佳範圍爲9 5 %以上。當 維持率超過90%時，瀝青系碳纖維之拉伸延伸度 高之理由並不十分清楚。過去之中間相瀝青之碳 經由液相。本發明之方法中，由於有必要將比過 之速度與 可使瀝青 輸送帶之 〜1 . 5 m /分 燒成獲得 、氪等惰 處理考量 爲批式處 以連續處 氧加成量 示之纖維 纖維長度 比過去更 化已知係 去更高濃 -19 - 201009146 度之氧加成於碳纖維前驅物上，而製作不融化纖維，故推 測碳纖維前驅物進行氧交聯，而不成爲自液相碳化變化成 固相碳化之原因》 [短纖維] 爲了使瀝青系碳纖維成爲期望之纖維長度，較好對所 得不織布進行切斷、破碎·粉碎等處理。又，依據情況， 亦可進行分級處理。處理方式係依據期望之纖維長度作選 @ 擇，但切斷較好使用斷頭台式、單軸、雙軸及多軸旋轉式 等切斷機。破碎、粉碎可適當的使用利用衝擊作用之鎚式 、針式、球式、珠粒式及棒式，利用顆粒彼此間之衝撞之 高速旋轉式，利用壓縮·撕裂作用之滾筒式、圓錐式及螺 旋式等破碎機·粉碎機等。 爲了獲得期望之纖維長度，亦可以多種複數機構成切 斷與破碎·粉碎。處理之氛圍爲濕式、乾式任一者均可。 分級處理可適當的使用振動篩式、離心分離式、慣性力式 @ 、過濾式等分級裝置等。期望之纖維長度不僅可藉由選定 機種，亦可藉由控制轉子·旋轉刀等之轉速、供給量、刀 刃間之間隙、系統內之滞留時間.等獲得。又，使用分級處 理時，期望之纖維長度可藉由調整篩網之孔徑等獲得。藉 由該等處理而成爲瀝青系碳短纖維。 以含有上述獲得之瀝青系碳纖維之不織布或藉由破碎 等獲得之瀝青系碳短纖維可進而在2,0 00〜3，5 00 °C下加熱 石墨化而成之最終含有瀝青系石墨化纖維之不織布或瀝青 -20- 201009146 系石墨化短纖維。石墨化係以Ache son爐、電爐等進行， 在真空中或使用氮氣、氬、氪等惰性氣體之非氧化性氛圍 等之中進行。 [毛氈] 本發明之不織布由於係由具有高延伸度及彈性率之瀝 青系碳纖維構成，因此適合於針扎處理，且可由本發明之 0 不織布適當的獲得毛氈。本發明包含藉由針扎處理上述不 織布獲得之毛氈。 本發明之毛氈之厚度方向之層間剝離強度較好爲 0.25N/5cm片以上，更好爲〇.35N/5cm片。層間剝離強度 小於0.25N/5cm片時，進行交叉捲棉之層合間之交織不完 全，加工時引起層間剝離，不僅因爲操作性變差，亦成爲 物性斑點之發生原因。其中，所謂的層間剝離強度爲顯示 毛氈之厚度方向之交織強度者。係由於毛氈厚度方向之中 φ 間位置以與層方向平行地切入刀刃，且以拉伸試驗機以 1 00mm/min之速度拉伸其兩端時之最大強度而求得。 構成本發明毛氈之碳纖維以光學顯微鏡觀測之平均纖 維徑較好大於2μιη、20μιη以下。平均纖維徑爲2μιη以下 時，由於空隙部分經細分化，因此有使成形加工時之樹脂 含浸性變差之情況。相反地，當平均纖維徑超過20μπι時 ，由於空隙部份變巨大化而使熱幅射之支配在強的高溫域 中之導熱性變大，因此有使隔熱性降低之情況。就耐氧化 性、強度提升之目的而言，尤其平均纖維徑之範圍較好爲 -21 - 201009146 大於ΙΟμιη且爲20μιη以下，更好爲大於1〇μιη且爲15μιη 以下。 本發明毛氈之基重量以250〜l，000g/m2較佳，基重量 可依據用途調整，但爲了安定且連續的生產，以 250〜 l,000g/m2最適當。當基重量小於250g/m2時，由於瀝青 系碳纖維織物變薄，因此經毛毵化處理有造成織物斷裂或 產生縐痕之情況。相反地，當基重量大於 1,00 〇g/m2時， 由於厚度變大，造成不融化處理時瀝青系不融化纖維織物 @ 之除熱無法順利進行，而有發生纖維彼此之間熔著等之情 況。基重量更佳之範圍爲400〜700g/m2。 因此本發明之毛氈較好其所構成之碳纖維之平均纖維 徑大於ΙΟμιη且爲20μιη以下，基重量爲2 5 0〜l，000g/m2。 本發明包含使上述毛氈進而在2,000~3,500 °C下熱處理獲 得之石墨化毛氈。 本發明之石墨化毛氈較好爲石墨化纖維之平均纖維徑 大於2μηι且爲20μηι以下，基重量爲250〜1，000g/m2。由 @ 於石墨化毛氈係由上述毛氈製造，因此基重量成爲自原先 之毛氈基重量減去因石墨化處理而減少之重量者。石墨化 毛氈之基重量可藉由選擇原先之毛氈基重量而適當的調整 〇 原先毛耗之基重量小於250g/m2時，由於瀝青系碳纖 維織物變薄，因此以毛氈化處理有使織物斷裂或出現縐痕 之情況。_相反地，當基重量大於l,000g/m2時，由於厚度 變大，造成不融化處理時瀝青系不融化纖維織物之除熱無 -22- 201009146 法順利進行，有發生纖維彼此之間熔著等之情況。基重量 之更佳範圍爲400〜700g/m2。 又，本發明之石墨化毛氈爲在空氣中以3 °C/分鐘升溫 之際之重量減少未達初期重量之1 〇wt%者較佳。重量減少 爲初期重量之l〇wt%以上時，耐氧化性顯著降低，無法充 分滿足作爲隔熱材使用時之特性而不佳。在空氣中以3 °C/ 分鐘升溫時之重量減少較好爲8wt%以下，更好爲5wt%以 下。又，在空氣中、以3°C/分鐘升溫時之重量減少可藉例 如熱示差重量分析器測定。 本發明之石墨化毛氈比由過去技術之毛氈製造之石墨 化毛氈之石墨化低。因此，導熱性低，作爲例如隔熱材使 用時，顯示優異之隔熱特性。本發明之石墨化毛氈之石墨 化性低之理由尙不十分清楚，但以本發明之方法，由於有 必要對碳纖維前驅物加成比過去更高濃度之氧，而製備不 融化纖維，故推測碳纖維前驅物進行氧交聯，而不成爲自 φ 液相碳化轉化成固相碳化之原因。 [毛氈之製造方法] 本發明包含毛氈之製造方法，該方法包含下列各步驟 (1 )將中間相瀝青進行紡絲，製造含有碳纖維前驅 物之前驅物織物[步驟（1)], (2)在氧化性氣體氛圍下不使前驅物織物融化，製 造含有氧加成量8〜15重量％之不融化纖維之不融化織物[ -23- 201009146 步驟（2 )]， (3) 使不融化織物在800~1,800°C下燒成製造不織布 [步驟（3 )]，及 (4) 將不織布進行針扎[步驟（4) ]» 步驟（1)至（3)係與上述不織布之製造方法相同。 但，相對於熱收縮以使步驟（2)與步驟（3)之輸送速度 比爲最適化較佳。過去，以熔融吹製法紡絲並捕集瀝青系 碳纖維，雖以了解以交叉棉捲之方法之生產性高，但交叉 @ 棉捲層合間交織有困難。其係爲了在經交叉棉捲之單層織 物經紡絲後之捕集之強交織，因此對層合者亦進行針扎處 理等毛酕化處理，而成爲碳纖維難以在厚度方向移行之起 因。另外由於碳纖維硬且脆，因此單純的刺扎數越多引起 纖維折損越多，反而使強度降低，且引起成品率降低。因 此爲使刺扎數不增多而交織，以使針之形狀最適化較佳。Further, Patent Document 6 describes that a carbon fiber having improved strength is produced by performing non-melting treatment in a temperature range of 100 to 400 ° C in an oxidizing atmosphere containing 0.1 to 40% by volume of Ν02 and 4 to 40% by volume of Η20. Production method. However, this method becomes a reduction in the modulus of elasticity as shown in the examples. As described above, it is extremely difficult to produce pitch-based carbon fibers having high elongation and high modulus of elasticity. (Patent Document 1) (Patent Document 3) (Patent Document 3) (Patent Document 4) (Patent Document 5) (Patent Document 5) Japanese Laid-Open Patent Publication No. Hei No. Hei 9-279 No. In the above-described manner, the carbon fiber having mesophase pitch as a raw material has an excellent modulus of elasticity, and conversely, The carbon fiber having an isotropic pitch as a raw material has a low tensile elongation and is difficult to carry out, for example, as a structural member for an industrial robot or an aircraft. Accordingly, it is an object of the present invention to provide a non-woven fabric containing pitch-based carbon fibers which has a tensile elongation which is disadvantageous of carbon fibers derived from mesophase pitch and which has high elongation and high modulus of elasticity which has not been used in the past. Further, the object of the present invention is to provide a felt which is subjected to a needle punching treatment of a nonwoven fabric containing a pitch-based carbon fiber having a high elongation and an elastic modulus, and a heat insulating material comprising the same. The present inventors have found that in the non-melting treatment in the carbon fiber production step using mesophase pitch as a raw material, a non-melting fiber having an oxygen addition amount of 8 to 15% by weight is produced, and is fired at 800 to 1,800 ° C. The present invention can be attained by obtaining a nonwoven fabric containing pitch-based carbon fibers having improved tensile elongation and having a high elongation which has not been high in the past and having a high modulus of elasticity. That is, the present invention encompasses the following invention. A non-woven fabric which is a non-woven fabric containing pitch-based carbon fibers, characterized in that the pitch-based carbon fibers are: (i) an average fiber diameter (D1) observed by an optical microscope is greater than 2 μm and is less than 20 μm, (Π) relative to The fiber diameter dispersion (S1) of the average fiber diameter (D1) observed by an optical microscope has a 100% yield of 3 to 20%, (iii) a tensile modulus of 80 to 300 GPa, and (iv) a tensile elongation of 1.4 to 1. 2.5%. 2. The nonwoven fabric according to the above 1, wherein the pitch-based carbon fiber has a tensile modulus of 100 to 300 GPa and a tensile elongation of 1.5 to 2.4%. 3. The nonwoven fabric according to the above 1, wherein the average fiber diameter (D1) of the pitch-based carbon fibers is greater than ΙΟμηη and is 20 μίη or less as observed by an optical microscope. 4. The nonwoven fabric according to the above 1, wherein the tensile strength is 10 N/5 cm or more. 201009146 5. A method for manufacturing a non-woven fabric, the method comprising the following steps (1) spinning a mesophase pitch to produce a precursor fabric containing a carbon fiber precursor, and (2) not making a precursor in an oxidizing gas atmosphere The fabric is melted to produce a non-melting fabric containing carbon fibers in an amount of 8 to 15% by weight, and (3) the unmelted fabric is fired at 800 to 1,800 °C. The production method according to the above 5, wherein the spinning is carried out by a melt blowing method. 7. The manufacturing method according to the above 5, wherein the carbon fiber precursor of the precursor fabric has an average fiber length of 4 to 25 cm. 8. The production method according to the above 5, wherein the carbon fiber of the non-melting fabric has an oxygen addition amount of 9 to 12% by weight. 9. The production method according to the above 5, wherein the fiber length maintenance ratio (%) expressed by the following formula (I) before and after the firing is 90% or more, and the φ fiber length maintenance ratio = 100x1^/1^° (1) L, Fiber length L1 before firing: fiber length after firing. 10. A felt is characterized in that it is obtained by subjecting the nonwoven fabric of the above 1 to a needle (n e e d 1 e p u n c h ) treatment. 1 1 . The hair β as described in the above 1 , has an interlayer peeling strength in the thickness direction of 〇.25 N/5 cm or more. 12. The gross loss according to the above 10, wherein the average fiber diameter of the carbon fibers is greater than ΙΟμηη and is less than 20 μm and the weight per unit area is 25 〇~201009146 1,000 g/m2 0 13. a graphitized felt is borrowed The heat loss described above was further obtained by heat treatment at 2,000 to 3,500 °C. A method for producing a felt, comprising the steps of: (1) spinning a mesophase pitch to produce a precursor fabric comprising a carbon fiber precursor, and (2) not causing a precursor fabric in an oxidizing gas atmosphere Melting, making a non-melting fabric containing carbon fibers having an oxygen addition amount of 8 to 15% by weight, (3) firing the unmelted fabric at 800-1,800 t, and (4) needle-bonding the non-woven fabric. 15. The manufacturing method according to the above 14, wherein the non-woven fabric is needle-punched with a needle having a depth of 0.15 mm or more and a number of lashes of 15 to 100 times/cm 2 . A composite body characterized by being impregnated with a resin in the felt described in the above paragraph. @17 - A composite body which is obtained by impregnating a graphitized felt according to the above 13 with a resin. A heat insulating material characterized by subjecting the composite according to the above 16 to heat treatment at 500 to 2,200 °C. 19. A method of producing a heat insulating material, comprising the steps of: (1) impregnating the felt of the above 10 with a resin to produce a composite: and -10- 201009146 (2) placing the composite at 500~ 2,200. 〇 Heat treatment. [Embodiment] [Non-woven fabric] The present invention is a nonwoven fabric comprising pitch-based carbon fibers. The pitch-based carbon fibers constituting the non-woven fabric are characterized by: (i) an average fiber diameter (D1) observed by an optical microscope of more than 2 μm and 20 μm or less, and (ii) a fiber diameter relative to an average fiber diameter (D1) observed by an optical microscope. The dispersion (S1) has a 100% yield of 3 to 20%, (iii) a tensile modulus of 80 to 300 GPa, and (iv) a tensile elongation of 1.4 to 2.5%. (Carbon Fiber: Tensile Elasticity and Tensile Elongation) Carbon fiber greatly changes its mechanical properties due to its firing temperature. Accordingly, the tensile modulus and tensile elongation of the crucible vary greatly due to the thermal experience in the carbon fiber manufacturing process. For example, carbon fibers using isotropic pitch as a raw material can sufficiently achieve an elongation of more than 1.4% in a wide temperature range from low temperature to high temperature. However, its modulus of elasticity is difficult to exceed 50 GP a. On the other hand, when the carbon fiber having the mesophase pitch as a raw material has a firing temperature of more than 800 °C, the modulus of elasticity may exceed 80 GPa. However, the past manufacturing methods have an extension of less than 1.4%. Further, when the firing temperature was less than 800 ° C, the elastic modulus of 80 GPa could not be achieved. These conventional techniques have difficulty in obtaining a pitch type -11 - 201009146 carbon fiber having a tensile modulus of 80 to 300 GPa and a tensile elongation of 1.4 to 2.5%. The present invention is characterized in that in the non-melting treatment in the production step of the pitch-based carbon fiber using the mesophase pitch as a raw material, 'the unmelted fiber is produced by the oxygen addition amount of 8 to 15% by weight, and the non-melting fiber is When it is fired at 800 to 1,800 ° C, it is possible to produce a pitch-based carbon fiber having a high tensile elongation which cannot be achieved in the past and having a high modulus of elasticity. The pitch-based carbon fiber constituting the non-woven fabric of the present invention has a tensile modulus of 80 to 300 GPa, preferably 100 to 300 GP, more preferably 180 to 300 GPa. The pitch-based carbon fiber constituting the non-woven fabric of the present invention has a tensile elongation of from 1.4 to 2.5%, preferably from 1.5 to 2.4%, more preferably from 1.6 to 2.3%. Therefore, the pitch-based carbon fiber constituting the non-woven fabric of the present invention preferably has a tensile modulus of 1 〇〇 to 300 GPa, a tensile elongation of 1.5 to 2.4%, a tensile modulus of 180 to 300 GPa, and a tensile elongation. The degree is 1.6~2.3%. (Carbon fiber: average fiber diameter (D1) and fiber diameter dispersion (S1)) The pitch-based carbon fiber constituting the nonwoven fabric of the present invention has a specific average fiber diameter (D1) because the tensile modulus and the tensile elongation are within the above range. And a ratio of 100 points of the fiber diameter dispersion (S1) with respect to the average fiber diameter (D1). The average fiber diameter (D1) of the pitch-based carbon fibers constituting the nonwoven fabric of the present invention was observed by an optical microscope to be more than 2 μm and not more than 20 μm. When the average fiber diameter is larger than ΙΟμηη and is 20 μm or less, it is preferably an oxidation resistance or an excellent strength. More preferably, it is larger than ΙΟμηι and is 15 μmη or less. The ratio of the fiber diameter dispersion (S1) of the average fiber diameter (D1) of the pitch-based -12-201009146 carbon fiber constituting the non-woven fabric of the present invention by an optical microscope is 3 to 20%, preferably 5 to 15%, Better for 8 to 13%. (Tensile Strength of Nonwoven Fabric) The tensile strength of the nonwoven fabric of the present invention is preferably 10 N/5 cm or more, more preferably 12 N/5 cm or more. When the tensile strength of the woven fabric is i 〇 N/5 cm or more, the tensile strength of the felt obtained by the molding treatment such as needle sticking can be improved. The felt can be used in the use of a heat insulating material such as a sound insulating material. The tensile strength of the nonwoven fabric was measured by a Tensilon measuring device, and a sample having a width of 5 cm x a length of 20 cm was stretched in the longitudinal direction. [Manufacturing method of non-woven fabric] The non-woven fabric of the present invention can be produced by the following steps: (1) Spinning mesophase pitch to produce a precursor fabric containing a carbon fiber precursor [Step (1)], φ (2) is oxidized The precursor fabric is not melted in a gas atmosphere, and an unmelted fabric containing carbon fibers in an amount of 8 to 15% by weight of oxygen is added [step (2)], and (3) the fabric is not melted at 800 to 1,800. (: Lower firing [Step (3) j 〇 The nonwoven fabric of the present invention containing pitch-based carbon fibers having high elongation and high modulus of elasticity can be obtained by this method. Hereinafter, each step of the present invention will be described in order. 13- 201009146 (Step (1): Spinning) The raw material of the pitch-based carbon fiber is preferably mesophase pitch. The mesophase ratio of the mesophase pitch is preferably 90% or more, more preferably 95% or more, and even more preferably 99. Further, the intermediate phase ratio of the mesophase pitch can be confirmed by observing the molten state by a polarizing microscope. The raw material of the mesophase pitch is exemplified by a condensed polycyclic hydrocarbon compound such as naphthalene or phenanthrene, such as petroleum pitch or coal carbon. A condensed heterocyclic compound of pitch, etc., wherein a condensed polycyclic hydrocarbon compound of naphthalene or phenanthrene is preferred. n Further, the softening point of the raw material pitch is preferably from 2,300 ° C to 3,400 ° C. The carbon fiber precursor It is necessary to treat the non-melting treatment at a temperature lower than the softening point. Therefore, when the softening point is lower than 203 °C, it is necessary to carry out the non-melting treatment at least at a low temperature which does not reach the softening point, and the result is not Melting needs On the other hand, when the softening point exceeds 340 °C, it is easy to cause thermal decomposition of asphalt, and the problem of gas generation in the filament is not good. The softening point range is better. It is more than 260 °C and above 3 2 °C, and it is better than 260 °C and above 3 10 °C. Moreover, the softening point of raw material leaching @青青 can be obtained by Mettler method. It is also possible to use two or more types as appropriate. The intermediate phase ratio of the raw material pitch of the combination is at least 90% or more, and the softening point is preferably 2,300 ° C or more and 3 4 0. (: The following. Step (1) The mesophase pitch spinning is carried out to produce a fabric containing a carbon fiber precursor precursor fabric. The spinning method is not particularly limited, and a so-called melt spinning method may be mentioned. Specifically, it is taken by a winder. The general spinning extension method of the mesophase pitch spouted by the die mouth, the melt blowing method using the hot air as the spray source, the centrifugation of the mesophase pitch by the centrifugal force, the -14-201009146 centrifugal spinning method, etc., wherein the type of the carbon fiber precursor is controlled. Reasons for improving production and other reasons The melt blowing method is preferably used. Hereinafter, the melt blowing method will be described. The shape of the spinning nozzle for forming the carbon fiber precursor in the present invention may be any. Usually, a true round shape is used, but an appropriate elliptical shape or the like is used. The shape of the nozzle is also no problem. The ratio of the length (LN) of the nozzle hole to the aperture (DN) (LN/DN) is preferably in the range of 2 to 20. When LN/DN exceeds 20, it will pass through the middle phase of the nozzle. φ Cyan exerts a strong shearing force to make the fiber profile appear as a radial structure. The appearance of the radial structure causes the fiber profile to be broken during the firing process, resulting in a decrease in mechanical properties. On the other hand, when LN/ When the DN is less than 2, it is impossible to impart shear to the raw material pitch, and as a result, it becomes a carbon fiber having low orientation. Therefore, it is not appropriate to produce excellent mechanical properties even if it is fired. In order to achieve excellent mechanical properties, a moderate shear force must be applied to the mesophase pitch. Accordingly, the ratio (LN/DN) of the length (LN) to the aperture (DN) of the nozzle hole is preferably in the range of 2 to 20, preferably in the range of 3 to 12. The nozzle temperature at the time of φ spinning, the shear rate when the mesophase pitch passes through the nozzle, the amount of air blown from the nozzle, the temperature of the wind, and the like are not particularly limited as long as the condition of the stable spinning state can be maintained, that is, the mesophase pitch The melt viscosity of the nozzle hole may be in the range of 1 to 100 Pa.s. When the melt viscosity of the mesophase pitch passing through the nozzle is less than IPa.s, the melt viscosity is too low to maintain the shape of the wire. On the other hand, when the melt viscosity of the intermediate phase asphalt exceeds 1 〇〇 Pa.s, the intermediate phase asphalt is subjected to a reinforced shear force', and a radial structure is formed in the fiber cross section. In order for the shear force applied to the mesophase pitch to be within an appropriate range and the dimension of the dimension -15-201009146 to be fibrous, it is necessary to control the melt viscosity of the mesophase pitch passing through the nozzle. Therefore, it is preferred that the melt viscosity of the mesophase pitch is preferably in the range of from 1 to 100 Pa·s, more preferably in the range of from 3 to 30 Pa.s and preferably in the range of from 5 to 25 Pa.s. The carbon fiber constituting the nonwoven fabric in the present invention is characterized in that the average fiber diameter (D1) is more than 2 μm and 20 μm or less. The control of the average fiber diameter of the carbon fiber can be adjusted by changing the pore size of the nozzle, or changing the amount of raw material pitch discharged from the nozzle or changing the draw ratio. The higher the draw ratio can be achieved by blowing a gas heated to @100~4()0° (: 100~20,000111 line speed per minute to the vicinity of the refinement point. The gas to be blown is not special.) Restriction, but in terms of cost-effectiveness and safety, air is more appropriate. The carbon fiber precursor is trapped on a conveyor belt such as a metal mesh to form a precursor fabric. At this time, the conveying speed by the conveyor belt can be Adjusted to an arbitrary basis weight, but can also be laminated by cross-rolling, etc. as needed. The basis weight of the precursor fabric is preferably 150 to 1,000 g/m2 in consideration of productivity and step stability. @碳纤维前前The average fiber length of the material is preferably in the range of 4 to 25 cm. When the average fiber length of the carbon fiber precursor is less than 4 cm, the strength of the fabric is significantly reduced before being trapped on a conveyor belt such as a metal mesh, and it is difficult to cross by adding The method of laminating cotton or the like causes lamination to cause a decrease in productivity. On the other hand, when it exceeds 25 cm, the precursor fabric is extremely bulky, and the reaction of the precursor fabric with the oxidizing gas is not melted in the subsequent step. It is difficult to remove, and it is not suitable according to the situation, such as burning. The average fiber length of the carbon fiber precursor is preferably 5~10cm. -16- 201009146 The average fiber diameter of the carbon fiber precursor obtained by spinning is better than 2 μιη When the average fiber diameter is 2 μm or less, it is difficult to control the oxygen addition amount in the step of producing an unmelted fiber having an oxygen addition amount of 8 to 15% by weight from the carbon fiber precursor. Therefore, the firing cannot be performed only because The carbon fiber obtained is of stable quality, and the carbon fiber precursor is not burned because the heat of reaction does not melt. On the other hand, when the average fiber diameter exceeds 20 μm, the oxygen addition amount from the carbon fiber precursor is 8-15. In the step φ of the % by weight non-melting fiber, it takes more time to produce an unmelted fiber having an oxygen addition amount of more than 8% by weight, resulting in a remarkable decrease in productivity. The average fiber diameter of the carbon fiber precursor is preferably in the range of It is larger than ΙΟμηη and is 20 μηη or less, more preferably larger than ΙΟμιη and 15 μιη or less. The fiber relative to the average fiber diameter of the carbon fiber precursor The 100% fraction of dispersion (S1) is preferably in the range of 3 to 20%. CV値 is an indicator of the dispersion of the fiber diameter, and in a small case, the stability of the step is high, meaning that the dispersion is small. However, the substantial CV is produced. In the case of less than 3% of the article, it is necessary to control the amount of the resin amount ejected from each capillary of the spinning nozzle as much as possible. Therefore, the spinning nozzle is made smaller, and as a result, significant productivity is caused by a decrease in the number of capillaries. On the other hand, in the case where the CV 値 is more than 20%, it is difficult to control the amount of oxygen addition from the step of producing the oxygen-added amount of the carbon fiber precursor in the amount of 7 to 15% by weight of the unmelted fiber, and the result is calcination. The quality of the pitch-based carbon fiber cannot be stabilized. The CV値 is better in the range of 8 to 15%. (Step (2): not melting) Step (2) is to produce a non-melting fabric containing carbon fibers having an oxygen addition amount of 8 to 15% by weight in order to prevent the precursor fabric from being melted in an oxidizing gas atmosphere. The steps. The present invention is characterized in that the non-melting fiber obtained in the step (2) has an oxygen addition amount of 8 to 15% by weight. When the oxygen addition amount of the non-melting fiber is less than 8% by weight, the tensile elongation of the carbon fiber obtained by firing in the step (3) may not exceed 1.4%. On the other hand, when the oxygen addition amount exceeds 15% by weight, the characteristic elastic modulus which is characteristic of the pitch-based carbon fiber using mesophase pitch as a raw material is remarkably lowered. The preferred oxygen addition amount for obtaining excellent tensile elongation and elasticity is in the range of 8 to 13% by weight, particularly preferably 9 to 12% by weight. The non-melting of the carbon fiber precursor is carried out in an oxidizing gas atmosphere. The so-called oxidizing gas system in the present invention means air or a mixed gas of gas and air which can extract electrons from the carbon fiber precursor. The gas which can extract electrons from the carbon fiber precursor can be exemplified by ozone, iodine, bromine, oxygen, and the like. However, in consideration of safety, convenience, and cost effectiveness, it is most appropriate to carry out the carbon fiber precursor in the air without melting. The non-melting of the carbon fiber precursor can be either a batch treatment or a continuous treatment, but continuous treatment is preferred in consideration of productivity. The melting temperature is preferably from 15 〇 to 35 〇 ° C, more preferably from 160 to 34 〇 ° C. The rate of temperature rise in the asphalt treatment should be 1 to 10 ° C / min. The preferred range of heating rate is 3 to 9 ° C / min taking into account the productivity and stability of the steps. In the case of continuous processing, the temperature increase rate can be achieved by sequentially setting a plurality of reaction chambers at any temperature. When the carbon fiber precursor is sequentially passed through a plurality of reaction chambers, a conveyor belt or the like can also be used. The amount of oxygen added to the non-melting fiber is related to the furnace temperature and the residence time in the furnace -18- 201009146. In the continuous treatment, it is preferred to control the temperature of each reaction chamber of the conveyor belt and control the residence time of each reaction chamber. The oxygen addition amount of the unmelted filament is preferably 8 to 15% by weight. The speed is also greatly related to the number of reaction chambers, but it is preferably a clock. (Step (3): firing) φ Step (3) is a step of making the non-melting fabric non-woven at 800 to 1,800 °C. The non-melting fabric is a non-woven fabric which is fired in a vacuum or in a non-oxidizing atmosphere using nitrogen gas or argon gas. The firing cost surface is preferably treated under normal pressure and a nitrogen atmosphere. Moreover, it is possible to handle either of the treatments and the continuous treatment, but it is more appropriate if the productivity is considered. When the non-melting fiber of the step (2) in the method of the present invention is 8 to 15% by weight, the length maintenance ratio (%) of the following formula (I) in the firing step may be 90% or more. Fiber length maintenance ratio = 100x1^/1^° (I) Fiber length before firing L1: Fiber length after firing The fiber length maintenance ratio is more preferably 95% or more. When the maintenance rate exceeds 90%, the reason why the tensile elongation of the pitch-based carbon fiber is high is not very clear. In the past, the carbon of the mesophase pitch passed through the liquid phase. In the method of the present invention, it is necessary to combine the speed of the ratio with the speed of the asphalt conveyor belt to be obtained, and the inert processing of the crucible is considered to be a continuous type of oxygen addition amount. The fiber length is more known than in the past. It is known that the higher concentration of -19 - 201009146 degrees of oxygen is added to the carbon fiber precursor, and the non-melting fiber is produced. Therefore, it is speculated that the carbon fiber precursor undergoes oxygen crosslinking without becoming a liquid phase. The reason why the carbonization changes to the solid phase carbonization. [Short fiber] In order to make the pitch-based carbon fiber a desired fiber length, the obtained nonwoven fabric is preferably subjected to a treatment such as cutting, crushing, and pulverization. Also, depending on the situation, classification processing is also possible. The treatment method is based on the desired fiber length, but the cutting machine such as the broken table, single shaft, double shaft and multi shaft rotary type is preferably used. For crushing and pulverizing, a hammer type, a needle type, a ball type, a bead type, and a rod type using impact, a high-speed rotary type in which particles collide with each other, and a drum type and a conical type which utilize compression and tear action can be suitably used. And spiral crushers, crushers, etc. In order to obtain the desired fiber length, it is also possible to form cut, crush and pulverize by a plurality of complex machines. The atmosphere of treatment can be either wet or dry. As the classification treatment, a vibrating screen type, a centrifugal separation type, an inertial force type @, a filtration type, and the like can be suitably used. The desired fiber length can be obtained not only by the selected model but also by controlling the number of revolutions of the rotor, the rotary blade, the amount of supply, the gap between the blades, and the residence time in the system. Further, when the classification treatment is used, the desired fiber length can be obtained by adjusting the pore diameter of the screen or the like. By these treatments, it becomes a pitch-based carbon short fiber. The non-woven fabric containing the pitch-based carbon fiber obtained above or the pitch-based carbon short fiber obtained by crushing or the like can be further graphitized by heating at 2,00 to 3,500 ° C to finally contain pitch-based graphitized fiber. Non-woven or bitumen-20- 201009146 is a graphitized short fiber. The graphitization is carried out in an Acheson furnace, an electric furnace or the like, and is carried out in a vacuum or in a non-oxidizing atmosphere using an inert gas such as nitrogen, argon or helium. [Felt] The nonwoven fabric of the present invention is suitable for needle-punching treatment because it is composed of asphalt-based carbon fibers having high elongation and elastic modulus, and can be suitably obtained from the 0-woven fabric of the present invention. The present invention comprises felt obtained by needle-punching the above-mentioned nonwoven fabric. The interlayer peel strength in the thickness direction of the felt of the present invention is preferably 0.25 N/5 cm or more, more preferably 〇. 35 N/5 cm. When the interlaminar peel strength is less than 0.25 N/5 cm, the interlacing between the cross-wound laminates is incomplete, and interlayer peeling occurs during processing, which is caused not only by the deterioration of workability but also by physical spots. Here, the interlaminar peel strength is an interlacing strength showing the thickness direction of the felt. The position is determined by cutting the blade in parallel with the layer direction in the thickness direction of the felt and maximizing the strength at the end of the tensile tester at a speed of 100 mm/min. The carbon fibers constituting the felt of the present invention have an average fiber diameter of more than 2 μm and 20 μm or less as observed by an optical microscope. When the average fiber diameter is 2 μm or less, the void portion is subdivided, so that the resin impregnation property during molding processing may be deteriorated. On the other hand, when the average fiber diameter exceeds 20 μm, the heat transfer property in the strong high temperature region is increased due to the increase in the void portion, so that the heat insulating property is lowered. For the purpose of oxidation resistance and strength improvement, the average fiber diameter is preferably in the range of -21 - 201009146 which is larger than ΙΟμηη and is 20 μm or less, more preferably more than 1 〇μιη and 15 μιη or less. The basis weight of the felt of the present invention is preferably 250 to 1,000 g/m2, and the basis weight can be adjusted depending on the use, but for stability and continuous production, 250 to 1,000 g/m2 is most suitable. When the basis weight is less than 250 g/m2, since the pitch-based carbon fiber fabric is thinned, the crepe treatment causes breakage or scarring of the fabric. On the other hand, when the basis weight is more than 1,00 〇g/m2, since the thickness becomes large, the heat of the asphalt-based unmelted fiber fabric is not smoothly performed in the non-melting treatment, and the fibers are fused to each other. The situation. The basis weight is preferably in the range of 400 to 700 g/m2. Therefore, the felt of the present invention preferably has a carbon fiber having an average fiber diameter of more than μμηη and 20 μm or less and a basis weight of 2,500 to 1,000 g/m2. The present invention comprises a graphitized felt obtained by heat-treating the above felt at 2,000 to 3,500 °C. The graphitized felt of the present invention preferably has a graphitized fiber having an average fiber diameter of more than 2 μm and a content of 20 μm or less and a basis weight of 250 to 1,000 g/m 2 . Since the @graphitized felt is made of the above felt, the basis weight is reduced from the weight of the original felt base minus the weight which is reduced by the graphitization treatment. The basis weight of the graphitized felt can be appropriately adjusted by selecting the weight of the original felt base. When the basis weight of the original felt is less than 250 g/m 2 , since the pitch-based carbon fiber fabric is thinned, the felting treatment may cause the fabric to break or A scar appears. _ Conversely, when the basis weight is greater than 1,000 g/m2, the thickness of the base is increased, and the heat removal of the asphalt-based unmelted fiber fabric during the non-melting treatment is not carried out smoothly, and the fibers are melted between each other. Waiting for the situation. A more preferred range of basis weight is from 400 to 700 g/m2. Further, the graphitized felt of the present invention is preferably a weight loss of less than 1% by weight of the initial weight when the temperature is raised at 3 °C/min in air. When the weight is reduced by more than 10% by weight of the initial weight, the oxidation resistance is remarkably lowered, and the characteristics when used as a heat insulating material are not sufficiently satisfied. The weight loss at a temperature of 3 ° C / min in air is preferably 8% by weight or less, more preferably 5% by weight or less. Further, the weight loss in air at a temperature rise of 3 ° C / minute can be measured by, for example, a thermal differential weight analyzer. The graphitized felt of the present invention has a lower graphitization than the graphitized felt made from the felt of the prior art. Therefore, the thermal conductivity is low, and when used as, for example, a heat insulating material, it exhibits excellent heat insulating properties. The reason why the graphitization felt of the present invention has low graphitization property is not fully understood. However, in the method of the present invention, since it is necessary to add a higher concentration of oxygen to the carbon fiber precursor than in the past, the non-melting fiber is prepared, so it is presumed that The carbon fiber precursor undergoes oxygen crosslinking without becoming a cause of conversion from φ liquid phase carbonization to solid phase carbonization. [Manufacturing Method of Felt] The present invention comprises a method for producing a felt comprising the following steps (1) of spinning a mesophase pitch to produce a precursor fabric containing a carbon fiber precursor [Step (1)], (2) In the oxidizing gas atmosphere, the precursor fabric is not melted, and an unmelted fabric containing an unmelted fiber having an oxygen addition amount of 8 to 15% by weight is produced [ -23- 201009146 Step (2)], (3) the unmelted fabric is made The nonwoven fabric is fired at 800 to 1,800 ° C [step (3)], and (4) the nonwoven fabric is needled [step (4)]» steps (1) to (3) are the same as the above-described nonwoven fabric manufacturing method . However, it is preferred to optimize the ratio of the transport speed of the step (2) to the step (3) with respect to heat shrinkage. In the past, spinning by a melt blowing method and trapping of pitch-based carbon fibers have been found to be highly productive, but it is difficult to interlace between the laps of the laps. In order to strongly interlace the single-layered fabric which has been cross-twisted after being spun, the laminate is also subjected to a burr-like treatment such as pinning treatment, which is a cause of difficulty in moving the carbon fibers in the thickness direction. Further, since the carbon fibers are hard and brittle, the more the number of simple puncturing, the more the fiber breaks, and the lower the strength, and the lower the yield. Therefore, it is preferable to optimize the shape of the needle so that the number of puncturing is not increased.
又由於使不融化織物燒成成爲不織布之際引起熱收縮 ，故若以連續製程製造，爲了使不融化織物在燒成時拉伸 G ，因此碳纖維在織物內呈緊張狀態。再者經常會有織物被 撕裂之狀態。碳纖維在織物內呈緊張狀態時，難以進行針 扎等毛氈化處理，而成爲纖維折損之原因，導致層間剝離 強度下降。據此，有必要採取使燒成處理時之熱收縮緩和 之措施，因此在步驟（2)(不融化）與步驟（3)(燒成 )之輸送速度比相對於熱收縮最適化較佳。亦即，步驟（ 2)之織物之輸送速度VI與步驟（（3)之織物之輸送速 度V2之比V1/V2以1.01〜1.10較佳。 -24- 201009146 步驟（4 )爲使不織度經針扎之步驟。針扎之刺扎數 較好爲1~200次/cm2，更好爲15~100次/cm2。針之繭絲 刺穿深度較好爲〇.15mm以上，更好爲0.2〜0.4mm。據此 ，步驟（4 )以使不織布以繭絲深度0.1 5mm以上之針，以 15〜100次/cm2之刺扎數之下進行針扎較佳。 當繭絲深度小於時，於刺扎數15〜100次/cm2 之範圍內之交織少，而無法獲得足夠之層間剝離強度。又 φ 當刺扎數小於1 5次/cm2時，即使繭絲深度在0· 1 5mm以 上，交織亦少，無法獲得足夠之層間剝離強度。相反地當 大於1 〇〇次/cm2時，纖維多數造成折損’強度下降，導致 成品率下降。繭絲深度更好之範圍爲〇.20mm以上，刺扎 數更好之範圍爲15~50次/cm2。 又，所謂繭絲深度係如圖1中所示’爲稱爲針之繭絲 之刺穿深度。又繭絲部亦具有稱爲具有彈起之突起。 經毛氈化處理之不織布之基重量、厚度等一起由針彈 φ 起高度、繭絲數、鄰接繭絲間隔、針深度予以適度選擇。 彈起高度可適當選自〇〜〇.15mm。彈起高度大於〇.15111111時 ，大多引起纖維折損’有強度下降、造成成品率下降之情 況。另外繭絲數可適度的選自3~18個之範圍。當繭絲數 少於3個時，交織變少’有無法獲得足夠之層間剝離強度 之情況。相反地當超過18個時’造成纖維多數折損’強 度下降，有造成成品率下降之情況。鄰接繭絲間隔可適當 的選自〇.3~3mm之範圍。另外’本發明之所謂鄰接繭絲間 隔爲包包含針板之不同列間鄰接者。鄰接繭絲間隔小於 -25- 201009146 0.3mm時，會造成多數纖維折損，有強度下降且造成成品 率下降之情況。相反地當超過3mm時，交織數變少，而 無法獲得足夠之層間剝離強度。針深度可適當的選自 0~20mm之範圍。針深度爲相對於毛氈顯示針突刺多深者 ，於與針扎時之底板與針前端之最短距離之繭絲（通稱爲 第一繭絲）之距離表示。針深度小於〇mm時，交織變少 ，有無法獲得足夠之層間剝離強度之情況。相反地當大於 20mm時，有引起纖維多數折損，強度下降，引起成品率 下降之情況。 圖1及圖2爲模式的顯示彈起高度、針深度、鄰接繭 絲間隔。 構成本發明之不織布之碳纖維由於具有高的延伸度及 高的彈性率，因此適於針扎處理。經由針扎獲得之毛氈鬆 密度爲0.01〜〇.5g/cm3，進而以0.03〜0.3g/cm3較佳。毛氍 之厚度只要是依據用途選擇即可而無特別限制，但例如爲 1〜100mm，較好爲5〜5 0mm左右。本發明之毛氈可較好地 使用於隔熱材、隔音材等。 [複合體] 本發明包含將樹脂含浸於上述毛氈中獲得之複合體。 樹脂以熱硬化性樹脂較佳。使熱硬化性樹脂含浸於毛氈中 ’且通常經加壓成形後，可經熱硬化獲得複合體。 至於熱硬化性樹脂舉例爲酚樹脂、環氧樹脂、丙烯酸 類、胺基甲酸酯類、矽氧類、醯亞胺類、熱硬化型改質之 -26- 201009146 PPE類、及熱硬化型PPE類、聚丁二烯橡膠及其共聚物、 丙烯酸系橡膠及其共聚物、矽氧系橡膠及其共聚物、天然 橡膠等，該等可單獨使用一種，亦可適當組合兩種以上使 用。樹脂之重量相對於1〇〇重量份之毛氈，較好爲 50〜1,000重量份，更好爲100〜700重量份。亦可使用上述 石墨化毛氈做爲上述毛氈。 參 [Ρι§熱材] 本發明包含使上述複合體在500〜2,200 °C下經熱處理 獲得之隔熱材。亦即，本發明之隔熱材可藉由（1)將樹 脂含浸於上述毛氈中製造複合體，（2)將上述複合體在 5 00〜2,200 °C下熱處理亦即碳化處理藉此而製造。此時之 熱處理亦即碳化處理之溫度以800 °C以上2,000°C以下較 佳。 如上述構成之碳纖維之平均纖維徑只要大於2 μιη且爲 • 20μιη以下之範圍即可，但尤其平均纖維徑大於10μιη且爲 20μιη以下，更好在ΙΟμιη且爲15μιη以下時成爲耐氧化性 或強度優異者，即使在高溫下亦難以氧化劣化，耐久性優 異，可較好地作爲高溫處理爐用之隔熱材。 隔熱材相對於100重量份之瀝青系碳纖維毛氈，含有 5 0〜1，〇〇〇重量份之碳化物。此處之碳化物意指使上述之複 合體經熱處理時使熱硬化性樹脂碳化獲得之成份。當碳化 物低於5 0重量份時，意指毛氈之空隙少，亦即毛氈之鬆 密度變高’導致隔熱性降低。相反地，當碳化物超過 -27- 201009146 1,000重量份時，隔熱材大部分爲源自熱硬化樹脂之碳化 物，成爲可期待耐氧化性之毛氈變少而非所需。較好相對 於100重量份之毛氈，碳化物爲100-700重量份。碳化物 與毛氈之重量比可自所得複合物之重量減掉預先測定之瀝 青系碳纖維毛氈重量之差，求得碳化物之重量，而自該等 計算出。 一般而言，隔熱材由於係在如高溫狀態之過度嚴苛條 件下使用，故要求有高的耐久性。本發明之由瀝青系碳纖 維構成之毛氈即使在高溫下亦難以氧化劣化，且即使作爲 複合材之狀態亦難以氧化劣化。據此，本發明之隔熱材由 於耐久性優異，因此亦可用於高溫處理之爐中。 實施例 以下藉由實施例更具體說明本發明，但本發明並不受 該等之任何限制。 實施例1 ~ 1 3與比較例1〜5中之各物性係以下列方法 測定。 (1)碳纖維之平均纖維徑（D1)與纖維徑分散（S1) 平均纖維徑（D1)係以光學顯微鏡，使用標度測定 60條碳纖維之纖維徑’且自其平均値求得。另外，CV値 爲所得平均纖維徑（D1)與纖維徑分散（si)之比率，且 由下式決定。 CV = S1/D1 X 1〇〇 201009146 其中 S 1^/((ΣΧ-Dl) 2/n) X爲觀測値，n爲觀 測數。 (2)碳纖維前驅物之平均纖維長度 碳纖維前驅物之平均纖維長度係以設置在模嘴下· 30cm之位置處之三支纖維捕集刷捕集碳纖維前驅物之束 ，測定該等束之長度且平均化而求得。 (3 )纖維長度維持率 由在800°C下燒成之碳纖維之纖維長度（L1)與燒成 前之纖維長度（L*5)之値，由下式（I)求得纖維長度維 持率。 纖維長度維持率=lOOxL1/；^ (I)Further, since the non-melting fabric is heat-shrinked when it is fired into a non-woven fabric, if it is produced in a continuous process, the carbon fiber is stretched in the fabric in order to stretch G during the firing. In addition, there is often a state in which the fabric is torn. When the carbon fiber is in a state of tension in the woven fabric, it is difficult to perform a felting treatment such as needle tying, which causes a fiber breakage, and the interlayer peel strength is lowered. Accordingly, it is necessary to take measures to alleviate the heat shrinkage during the baking treatment. Therefore, the conveying speed in the step (2) (not melting) and the step (3) (baking) is preferably optimized over the heat shrinkage. That is, the ratio of the conveying speed VI of the fabric of the step (2) to the ratio V1/V2 of the conveying speed V2 of the fabric of (3) is preferably 1.01 to 1.10. -24- 201009146, the step (4) is for the non-wovenness. The step of needle sticking is preferably 1 to 200 times/cm 2 , more preferably 15 to 100 times/cm 2 . The piercing depth of the needle is preferably more than 15 mm, more preferably 0.2 to 0.4 mm. Accordingly, the step (4) is preferably performed so that the non-woven fabric has a needle having a depth of 0.1 5 mm or more, and is preferably needled under the number of lashes of 15 to 100 times/cm 2 . , the interlacing in the range of 15 to 100 times/cm 2 is less, and sufficient interlaminar peel strength cannot be obtained. φ When the number of punctures is less than 15 times/cm 2 , even if the depth of the twist is 0·15 mm Above, the interlacing is also small, and sufficient interlayer peel strength cannot be obtained. Conversely, when it is more than 1 〇〇/cm2, most of the fibers cause a decrease in the strength of the fracture, resulting in a decrease in the yield. The range of the twist depth is preferably 〇.20 mm. Above, the range of the number of pricking is better is 15~50 times/cm2. Moreover, the so-called silk depth is as shown in Fig. 1 'is the silk called the needle The depth of penetration is also called a protrusion with a bounce. The weight and thickness of the non-woven fabric of the felting process are moderately determined by the height of the needle φ, the number of turns, the spacing of the adjacent turns, and the depth of the needle. The height of the bounce can be appropriately selected from 〇~〇.15mm. When the bounce height is greater than 〇.15111111, most of the fiber breakages are caused by the decrease in strength and the decrease in yield. The number of crepe is moderately selected from 3 ~18 ranges. When the number of twisted yarns is less than 3, the interlacing becomes less. 'There is not enough interlayer peel strength. If the number exceeds 18, the 'majority of the fiber' is reduced, resulting in a finished product. The rate of decrease in the rate of adjacent filaments may be suitably selected from the range of 〇3 to 3 mm. In addition, the so-called adjacent filament spacing of the present invention is an adjacency between different columns including a needle plate. The spacing between adjacent filaments is less than - 25-201009146 0.3mm, it will cause most fiber breakage, and the strength will decrease and the yield will drop. On the contrary, when it exceeds 3mm, the number of interlaces will be less, and sufficient interlayer peeling will not be obtained. The depth of the needle can be suitably selected from the range of 0 to 20 mm. The depth of the needle is the length of the needle that is perpendicular to the felt, and the shortest distance between the bottom of the needle and the front end of the needle (referred to as the first flaw) The distance between the filaments indicates that when the needle depth is less than 〇mm, the interlacing becomes less, and there is a case where sufficient interlayer peel strength cannot be obtained. Conversely, when it is larger than 20 mm, the fiber is mostly broken, the strength is lowered, and the yield is lowered. Fig. 1 and Fig. 2 show the height of the pop-up, the depth of the needle, and the spacing of the adjacent filaments in the mode. The carbon fiber constituting the nonwoven fabric of the present invention is suitable for the needle sticking treatment because of its high elongation and high modulus of elasticity. The felt density obtained by needle sticking is 0.01 to 5.5 g/cm3, and further preferably 0.03 to 0.3 g/cm3. The thickness of the bristles is not particularly limited as long as it is selected depending on the use, but is, for example, 1 to 100 mm, preferably about 5 to 50 mm. The felt of the present invention can be preferably used for a heat insulating material, a sound insulating material or the like. [Composite] The present invention comprises a composite obtained by impregnating a resin with the above felt. The resin is preferably a thermosetting resin. The thermosetting resin is impregnated into the felt' and usually after compression molding, the composite can be obtained by heat hardening. Examples of the thermosetting resin are phenol resin, epoxy resin, acrylic, urethane, oxime, quinone, thermosetting type -26-201009146 PPE, and thermosetting PPE. The type, the polybutadiene rubber and the copolymer thereof, the acrylic rubber and the copolymer thereof, the oxime rubber and the copolymer thereof, and the natural rubber may be used singly or in combination of two or more kinds as appropriate. The weight of the resin is preferably from 50 to 1,000 parts by weight, more preferably from 100 to 700 parts by weight, per part by weight of the felt. The above graphitized felt can also be used as the above felt. Reference [Ρι§热材] The present invention comprises a heat insulating material obtained by subjecting the above composite to heat treatment at 500 to 2,200 °C. That is, the heat insulating material of the present invention can be manufactured by (1) impregnating the resin into the felt to produce a composite, and (2) heat-treating the composite at 500 ° C, 200 ° C, that is, carbonizing. . The heat treatment at this time, that is, the temperature of the carbonization treatment is preferably 800 ° C or more and 2,000 ° C or less. The average fiber diameter of the carbon fiber having the above-described configuration may be in the range of more than 2 μm and not more than 20 μm, but particularly, the average fiber diameter is more than 10 μm and is 20 μm or less, and more preferably oxidized or strong when ΙΟμηη and 15 μm or less. Excellent, it is difficult to oxidize and degrade even at a high temperature, and it is excellent in durability, and can be suitably used as a heat insulating material for a high-temperature processing furnace. The heat insulating material contains 50 to 1 part by weight of the carbide of 100 parts by weight of the pitch-based carbon fiber felt. The carbide herein means a component obtained by carbonizing a thermosetting resin when the above composite is heat-treated. When the amount of the carbonized material is less than 50 parts by weight, it means that the void of the felt is small, that is, the bulk density of the felt becomes high, resulting in a decrease in heat insulating property. On the other hand, when the amount of the carbide exceeds -27 - 201009146 1,000 parts by weight, the heat insulating material is mostly a carbonized material derived from a thermosetting resin, and the felt which is expected to have oxidation resistance is reduced rather than required. Preferably, the carbide is from 100 to 700 parts by weight relative to 100 parts by weight of the felt. The weight ratio of carbide to felt can be calculated from the weight of the obtained composite minus the difference in weight of the previously determined asphaltic carbon fiber felt to determine the weight of the carbide. In general, heat insulating materials are required to have high durability because they are used under excessively severe conditions such as high temperature. The felt composed of the pitch-based carbon fiber of the present invention is hardly oxidatively degraded even at a high temperature, and is hardly oxidized and deteriorated even in the state of the composite material. Accordingly, the heat insulating material of the present invention can be used in a furnace for high temperature treatment because of its excellent durability. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited thereto. Each of the physical properties of Examples 1 to 13 and Comparative Examples 1 to 5 was measured by the following method. (1) Average fiber diameter (D1) and fiber diameter dispersion (S1) of carbon fiber The average fiber diameter (D1) was determined by an optical microscope using a fiber diameter of 60 carbon fibers using a scale and obtained from the average. Further, CV 値 is the ratio of the obtained average fiber diameter (D1) to the fiber diameter dispersion (si), and is determined by the following formula. CV = S1/D1 X 1〇〇 201009146 where S 1^/((ΣΧ-Dl) 2/n) X is the observed 値 and n is the observed number. (2) Average fiber length of carbon fiber precursor The average fiber length of the carbon fiber precursor is a bundle of carbon fiber precursors collected by three fiber-collecting brushes placed at a position of 30 cm below the nozzle, and the length of the bundles is measured. And averaged and obtained. (3) Fiber length maintenance ratio The fiber length maintenance ratio was determined from the following formula (I) from the fiber length (L1) of the carbon fiber fired at 800 ° C and the fiber length (L * 5) before firing. . Fiber length maintenance rate = lOOxL1/; ^ (I)
Ll燒成前之纖維長度 L1:燒成後之纖維長度 ® 而且，碳纖維之纖維長度（L1)爲自在8 00 °C下燒成 之不織布抽取出1〇條，且量測其長度並以經平均化予以 評價。另外，燒成前之纖維長度（LG)係自不融化織物抽 取出1 0條，並經平均化予以評價。 (4)不融化纖維之氧加成量 不融化纖維之氧加成量係以CHNS-O分析儀（Thermo ELECTRON CORPORATION 製造之 FLASH EA 1 1 12 系歹Ij )測定。 -29- 201009146 (5) 碳纖維之拉伸延伸度、拉伸彈性率、不織布之拉伸 強度 碳纖維之拉伸延伸度、拉伸彈性率係拉伸1 20條碳纖 維絲，測定各纖維徑後，以 TENSILON測定裝置（ ORIENTEC RTC-1150A)測定120條之機械強度，且求得 拉伸延伸度、拉伸彈性率之總平均値予以決定。 鑤 (6) 不織布之拉伸強度 自不織布於寬度方向，由左、中、右各兩點合計六點 抽取寬度 5cmx長度20cm之樣品，且以拉伸試驗機在 100mm/min之速度下於長度方向拉伸，計算出其強度平均 値予以決定。 (7) 毛氈之層間剝離強度 自不織布於寬度方向，由左、中、右各兩點合計六點 Θ 抽取寬度5cmx長度l〇cm之樣品’且以與層方向平行地將 刀刃插入樣品厚度方向中間位置並切開，自以拉伸試驗機 在100mm/min之速度下拉伸其兩端時之最大強度之平均値 求得。 (8 )毛氈之基重量 自毛毵於寬度方向，由左、中、右各兩點合計六點進 行A4大小之切割，且測量其重量計算出基重。 -30- 201009146 (9)隔熱材之拉伸強度 以大型特性試驗裝置（東洋BALDWIN製造，SS-207-5P)測定。 (1 〇 )與酚系樹脂之複合材料之剖面 以掃描電子顯微鏡在1，000倍之倍率下觀察，確認空 φ 隙。 (11) 隔熱材之熱傳導率 使用京都電子製造之QTM-5 00，以探針法求得。 (12) 碳化物與碳纖維毛氈之重量比 自所得複合物之重量扣除預先測定之碳纖維毛氈之重 量，求得碳化物之重量並計算出。 (1 3 )石墨化毛氈之耐氧化性 使用熱示差重量分析裝置（理學電機製造，TG8 120) ，在空氣中自室溫以3°C/分鐘升溫’評價700°C下之重量 減少量。 實施例1 (紡絲） 在335 °C下，使用由直徑〇.2mm<^、長度2mm之毛細 201009146 管構成之模嘴，自毛細管橫向之狹長口將每分鐘8,000m 之3 3 9°C空氣吹送至由芳香族烴構成之中間相率100%、軟 化溫度278 °C之中間相瀝青，將熔融之中間相瀝青拉伸， 製造平均直徑13.Ομηι之含碳之前驅物織物。以金屬刷捕 集模嘴正下方之碳纖維前驅物，確認其平均纖維長度爲 8.4cm。 (不融化） ❻ 接著，在空氣氛圍中，於30分鐘內使前驅物織物自 200°C升溫至3 40 °C，製造由不融化纖維構成之不融化織物 。不融化纖維之氧加成量爲10.9重量％。又，不融化纖維 之平均纖維長度爲8.5cm。 (燒成） 接著連續在氮氣氛圍中於8 00 °C下進行燒成處理，製 造由碳纖維組成之不織布。此時，不融化處理時之織物之 〇 輸送速度VI與燒成處理時之織物之輸送速度V2之比 V1/V2爲1.03。所得碳纖維之平均纖維徑爲12.1μπι，纖 維徑之CV値爲10.2%。又，碳纖維之平均纖維長度爲 8.1cm，纖維長度維持率爲95%。而且，測定由碳纖維組 成之不織布之拉伸延伸強度爲15.5 N/5 cm片。 另外，使不融化織物在氬氣氣體氛圍中，於1小時內 自室溫燒成至1,500°C，獲得由碳纖維構成之不織布。評 價該碳纖維之機械特性後，拉伸延伸度爲1 . 6 1 %，拉伸強 -32- 201009146 度爲3.0GPa’拉伸彈性率爲24〇Gpa。 實施例2 (毛氈） 使用彈起筒度0.05mm、繭絲數9個、 3mm、繭絲深度〇_25mm之針，在刺扎數20 度1 0mm下對由實施例1獲得之碳纖維組成 針扎處理獲得毛氈。所得毛氈之層間 Φ 0.45N/5cm片，平均纖維徑爲12.1 μιη，基重 實施例3(複合體〜隔熱材） 將實施例2中製造之毛氈浸漬於酚樹脂 股）製造，PL-2211，黏度 O.lPa· s)中， 縮榨出多餘之酚樹脂後，於250 °C下成形J 8〇〇°C下燒成。接著，在2,000°C下熱處理， φ 維之隔熱材。相對於100重量份之碳纖維毛 重量份之碳化物。觀察燒成體之剖面後未觀 熱材之拉伸強度爲0.74MPa，熱傳導率爲〇. 在2,000°C、氧濃度20ppm下處理24小時後 0.68MPa ° 實施例4(石墨化毛氈）L1 fiber length before firing L1: fiber length after firing® Moreover, the fiber length (L1) of the carbon fiber is one strip extracted from the non-woven fabric fired at 800 ° C, and the length is measured and measured by Averaging is evaluated. Further, the fiber length (LG) before firing was taken out from the non-melted fabric and evaluated by averaging. (4) Oxygen addition amount of non-melting fiber The oxygen addition amount of the non-melting fiber was measured by a CHNS-O analyzer (FLASH EA 1 1 12 system 歹Ij manufactured by Thermo ELECTRON CORPORATION). -29- 201009146 (5) Tensile elongation, tensile modulus, tensile strength of non-woven fabric, tensile elongation of carbon fiber, tensile modulus of elasticity, stretching of 20 carbon fiber filaments, after measuring the fiber diameter, The mechanical strength of 120 pieces was measured by a TENSILON measuring device (ORIENTEC RTC-1150A), and the total average 値 of the tensile elongation and the tensile modulus of elasticity was determined.鑤(6) The tensile strength of the non-woven fabric is not woven in the width direction. A total of six points from the left, the middle and the right are extracted at a height of 5 cm and a length of 20 cm. The tensile tester is used at a speed of 100 mm/min. The direction is stretched and the average intensity is calculated. (7) The interlaminar peeling strength of the felt is not woven in the width direction, and the total of the left, middle and right points is six points. The sample with a width of 5 cm x length l〇cm is extracted and the blade is inserted into the thickness direction of the sample in parallel with the layer direction. The middle position was cut and cut, and the average strength of the maximum strength when the tensile tester was stretched at a speed of 100 mm/min was obtained. (8) Base weight of felt From the width direction of the hair, the A4 size is cut by a total of six points from the left, middle and right points, and the weight is calculated to calculate the basis weight. -30- 201009146 (9) Tensile strength of heat-insulating material Measured with a large-scale characteristic tester (manufactured by Toyo BALDWIN, SS-207-5P). Cross section of the composite material of (1 〇) and phenolic resin was observed at a magnification of 1,000 times by a scanning electron microscope to confirm the empty φ gap. (11) Thermal conductivity of heat-insulating material The QTM-5 00 manufactured by Kyoto Electronics was used to obtain the probe method. (12) Weight ratio of carbide to carbon fiber felt The weight of the obtained composite was subtracted from the weight of the previously determined carbon fiber felt, and the weight of the carbide was determined and calculated. (1 3 ) Oxidation Resistance of Graphitized Felt The weight loss at 700 ° C was evaluated by using a differential differential weight analyzer (manufactured by Rigaku Electric Co., Ltd., TG8 120) at a temperature of 3 ° C / min from room temperature in air. Example 1 (spinning) At 335 ° C, a nozzle composed of a capillary diameter of 〇.2 mm <^, length 2 mm, 201009146 tube was used, and the narrow opening from the lateral direction of the capillary would be 8,000 m 3 3 9 ° C per minute. The air is blown to a mesophase pitch composed of an aromatic hydrocarbon having an intermediate phase ratio of 100% and a softening temperature of 278 °C, and the molten mesophase pitch is stretched to produce a carbon-containing precursor fabric having an average diameter of 13. Ομηι. The carbon fiber precursor immediately below the nozzle was collected with a metal brush to confirm that the average fiber length was 8.4 cm. (No melting) ❻ Next, the precursor fabric was heated from 200 ° C to 3 40 ° C in an air atmosphere for 30 minutes to produce a non-melting fabric composed of non-melting fibers. The oxygen addition amount of the non-melted fiber was 10.9% by weight. Further, the average fiber length of the non-melted fiber was 8.5 cm. (Calcination) Next, the baking treatment was continuously performed at 800 ° C in a nitrogen atmosphere to produce a nonwoven fabric composed of carbon fibers. At this time, the ratio V1/V2 of the woven conveying speed VI of the fabric at the time of the non-melting treatment to the conveying speed V2 of the fabric during the baking treatment was 1.03. The obtained carbon fibers had an average fiber diameter of 12.1 μm and a fiber diameter of CV値 of 10.2%. Further, the carbon fiber had an average fiber length of 8.1 cm and a fiber length maintenance ratio of 95%. Further, the tensile elongation of the non-woven fabric composed of carbon fibers was measured to be 15.5 N/5 cm. Further, the non-melting fabric was fired from room temperature to 1,500 ° C in an argon gas atmosphere for 1 hour to obtain a nonwoven fabric composed of carbon fibers. After evaluating the mechanical properties of the carbon fiber, the tensile elongation was 1.61%, and the tensile strength was -32-201009146 degrees, and the tensile modulus was 3.0 〇Gpa. Example 2 (Felt) A needle composed of carbon fiber obtained in Example 1 was used at a needle length of 0.05 mm, a number of twisted yarns of 9, 3 mm, and a thread having a depth of 〇 25 mm, at a number of puncturings of 20 degrees and 10 mm. The felt is obtained by the tie. Between the layers of the obtained felt Φ 0.45 N/5 cm, the average fiber diameter was 12.1 μηη, and the basis weight Example 3 (composite to heat-insulating material). The felt produced in Example 2 was immersed in a phenol resin strand), PL-2211 In the viscosity O.lPa·s), after the excess phenol resin is squeezed out, it is fired at a temperature of 250 ° C at J 8 ° C. Next, heat treatment at 2,000 ° C, φ dimensional heat insulation material. Carbide in parts by weight relative to 100 parts by weight of carbon fiber. After observing the cross section of the fired body, the tensile strength of the hot material was 0.74 MPa, and the thermal conductivity was 〇. After treating at 2,000 ° C for 20 hours at an oxygen concentration of 20 ppm, 0.68 MPa ° Example 4 (graphitized felt)
在氬氣氛圍中，將實施例2製造之毛氈 室溫燒成至2,0001，獲得石墨化毛氈。基S 鄰接繭絲間隔 次/cm2，針深 之不織布進行 剝離強度爲 量爲 445g/m2 (群榮化學（ 且以輥壓機壓 丧複合體，在 獲得含有碳纖 氈，含有400 察到空隙。隔 048W/m . K。 之拉伸強度爲 3小時內自 量爲 438g/m2 -33- 201009146 ，構成石墨化毛氈之單絲之平均纖維徑爲1 1.3 μιη。又， 使石墨化毛氈在空氣中，自室溫以3°C/分鐘升溫至700。(： 之際之於7〇〇 °C下之重量減少爲初期重量之4.8 wt%。 實施例5 (石墨化毛氈〜隔熱材） 將實施例4中製造之石墨化毛氈浸漬於酚樹脂（群榮 化學（股）製造，PL-221 1，黏度O.lPa . s )中，以輥壓 機壓縮榨出多餘之酚樹脂後，於250 °C下成形成複合體， 在800 °C下燒成。接著，在2,000°C下熱處理，獲得含有 石墨化纖維之隔熱材。相對於1 〇〇重量份之石墨化纖維毛 氈，碳化物含有405重量份。觀察燒成體之剖面後未觀察 到空隙。隔熱材之拉伸強度爲 1.23MPa，熱傳導率爲 0.078W/m· K。在2,000°C、氧濃度20ppm下處理24小時 後之拉伸強度爲1.18MPa。The felt produced in Example 2 was fired at room temperature to 2,000 in an argon atmosphere to obtain a graphitized felt. The base S was adjacent to the crepe spacing/cm2, and the non-woven fabric of the needle depth was subjected to a peeling strength of 445 g/m2 (Group Rong Chemical (and a compacted body by a roll press, and a carbon fiber felt was obtained, and 400 voids were observed. The tensile strength is 048 W/m. K. The tensile strength is 438 g/m2 -33-201009146 in 3 hours, and the average fiber diameter of the monofilament constituting the graphitized felt is 13.1 μηη. Further, the graphitized felt is in the air. The temperature was raised from room temperature to 3 ° C / min to 700. (: The weight loss at 7 ° C was 4.8 wt % of the initial weight. Example 5 (graphitized felt ~ heat insulation material) The graphitized felt produced in Example 4 was immersed in a phenol resin (manufactured by Qun Rong Chemical Co., Ltd., PL-221 1, viscosity O.lPa.s), and the excess phenol resin was compressed and squeezed by a roll press. The composite was formed at 250 ° C and fired at 800 ° C. Then, heat treatment was carried out at 2,000 ° C to obtain a heat insulating material containing graphitized fibers. Carbonization was carried out with respect to 1 part by weight of graphitized fiber felt. The content contained 405 parts by weight. No void was observed after observing the cross section of the fired body. The tensile strength was 1.23 MPa, and the thermal conductivity was 0.078 W/m·K. The tensile strength after treatment at 2,000 ° C and an oxygen concentration of 20 ppm for 24 hours was 1.18 MPa.
實施例6 Q (紡絲） 在331°C下，使用由直徑、長度2mm之毛細 管構成之模嘴，自毛細管橫向之狹長口將每分鐘8,000m 之3 3 6°C空氣吹送至由芳香族烴構成之中間相率100%、軟 化溫度278。(：之中間相瀝青’將熔融之中間相瀝青拉伸， 製造平均直徑1 1.0 μ®之前驅物織物。以金屬刷收集模嘴 正下方之碳纖維前驅物’確認其平均纖維長度爲15.3 cm» -34- 201009146 (不融化） 接著，在空氣氛圍中，於30分鐘內使前驅物織物自 200°C升溫至34(TC，製造由不融化纖維構成之不融化織物 。不融化纖維之氧加成量爲11.8重量％。又，不融化纖維 之平均纖維長度爲15.2cm。 (燒成） 接著連續在氮氣氛圍中於800°C下進行燒成處理，製 造由碳纖維組成之不織布。此時，不融化處理時之織物之 輸送速度 VI與燒成處理時之織物之輸送速度V2之比 V1/V2爲1.02。所得碳纖維之平均纖維徑爲10.3μιη，纖 維徑之CV値爲 8.2%。又，碳纖維之平均纖維長度爲 14.2 cm，纖維長度維持率爲93%。而且，測定由碳纖維組 成之不織布之拉伸延伸強度爲14 ·6Ν/5 cm片。 另外，使所得不融化織物在氬氣氣體氛圍中，於1小 # 時內自室溫燒成至1，500 °C，獲得由碳纖維構成之不織布 。評價該碳纖維之機械特性後，拉伸延伸度爲1.55%，拉 伸強度爲3.1GPa，拉伸彈性率爲23 5 GPa。 實施例7 (毛氈） 使用彈起高度〇.〇4mm、繭絲數9個、鄰接繭絲間隔 3mm、繭絲深度0.20mm之針，在刺扎數25次/cm2、針深 度10mm下對由實施例6獲得之碳纖維組成之不織布進行 針扎處理獲得毛氈。所得毛氈之層間剝離強度爲 -35- 201009146 0.48N/5cm片，平均纖維徑爲1〇·5μιη，基重量爲3 90g/m2 實施例8 (複合體〜隔熱材） 將實施例7中製造之毛氈浸漬於酚樹脂（群榮化學（ 股）製造，PL-2211，黏度O.lPa· s)中，以輥壓機壓縮 榨出多餘之酚樹脂後，於25 0 °C下成形成複合體，在800 °C下燒成。接著，在2,000 °C下熱處理，獲得含有碳纖維 之隔熱材。相對於1〇〇重量份之毛氈，含有400重量份之 碳化物。觀察燒成體之剖面後未觀察到空隙。隔熱材之拉 伸強度爲〇.79MPa，熱傳導率爲0.049W/m. K。在2,000 °C 、氧濃度 20ppm下處理 24小時後之拉伸強度爲 0.76MPa ° 實施例9 (石墨化毛氈） 在氬氣氛圍中，將實施例7製造之毛氈於3小時內自 @ 室溫燒成至2,5 00°C，獲得石墨化毛氈。基重量爲3 8 5 g/m2 ，構成石墨化毛氈之單絲之平均纖維徑爲9.8 μιη。又，使 石墨化毛氈在空氣中，自室溫以3 °C/分鐘升溫至700 °C之 際之於700 °C下之重量減少爲初期重量之3.8 wt%。 實施例1 0 (紡絲） 在336°c下，使用由直徑〇.2ιηιηφ、長度2mm之毛細 -36- 201009146 管構成之模嘴，自毛細管橫向之狹長口將每分鐘5,000m 之3 3 9 t空氣吹送至由芳香族烴構成之中間相率1 〇〇%、軟 化溫度278°C之中間相瀝青，將熔融之中間相瀝青拉伸， 製造平均直徑15.1 μιη之由碳纖維前驅物構成之前驅物織 物。以金屬刷捕集模嘴正下方之碳纖維前驅物，確認其平 均纖維長度爲l〇.4cm。 (不融化） 接著，在空氣氛圍中，於30分鐘內使前驅物織物自 200°C升溫至340°C，製造由不融化纖維構成之不融化織物 。不融化纖維之氧加成量爲8.4重量％。又，不融化纖維 之平均纖維長度爲10.4cm。 (燒成） 接著連續在氮氣氛圍中於800t下進行燒成處理，製 φ 造由碳纖維組成之不織布。此時，不融化處理時之織物之 輸送速度 VI與燒成處理時之織物之輸送速度 V2之比 V1/V2爲1.04。碳纖維之平均纖維徑爲14.3μιη，纖維徑 之CV値爲10.5%。又，碳纖維之平均纖維長度爲9.5cm ，纖維長度維持率爲91%。而且，測定由碳纖維組成之不 織布之拉伸延伸強度爲15.6N/5cm片。又，使由不融化纖 維構成之不織物在氬氣氣體氛圍中，於1小時內自室溫燒 成至1，500 °C，獲得由碳纖維構成之不織布。評價該碳纖 維之機械特性後，拉伸延伸度爲1.48%，拉伸強度爲 -37- 201009146 2.6GPa，拉伸彈性率爲25 3 GPa。 實施例1 1 (毛酕） 使用彈起高度0 · 0 5 m m、繭絲數9個、鄰接繭絲間隔 3 mm、繭絲深度爲〇 · 3 0mm之針’在刺扎數3 0次/cm2、針 深度10mm下對由實施例1〇獲得之碳纖維組成之不織布 進行針扎處理獲得毛氈。所得毛氈之層間剝離強度爲 0.39N/5cm片，平均纖維徑爲14.3μιη，基重量爲460g/m2 _ 實施例12 (複合體〜隔熱材） 將實施例11中製造之毛氈浸漬於酚樹脂（群榮化學 (股）製造，PL-4222，黏度0.5Pa . s )中，以輥壓機壓 縮榨出多餘之酚樹脂後，於250 °C下成形成複合體，在 8〇〇°C下燒成。接著，在2,000°C下熱處理，獲得含有碳纖 維之隔熱材。相對於100重量份之碳纖維毛氈，含有400 Q 重量份之碳化物。觀察燒成體之剖面後未觀察到空隙。隔 熱材之拉伸強度爲0_83MPa，熱傳導率爲0.049W/m. K。 在2,000°C、氧濃度20ppm下處理24小時後之拉伸強度爲 0.78MPa ° 實施例13 (石墨化毛氈） 在氬氣氛圍中，將實施例11製造之毛氈於3小時內 自室溫燒成至3,000 °C ，獲得石墨化毛氈。基重量爲 -38 - 201009146 452g/m2，構成石墨化毛劃之單絲之平均纖維徑爲13·8μηι 。又，使石墨化毛氈在空氣中，自室溫以3 °C/分鐘升溫至 7〇〇。(：之際之於7〇〇°C下之重量減少爲初期重量之3.lwt% 比較例1 (紡絲） φ 在335。(：下，使用由直徑〇.2ιηπιφ、長度2mm之毛係 管構成之模嘴，自毛細管橫向之狹長口將每分鐘8,000m 之339 °C空氣吹送至由芳香族烴構成之中間相率iOO%、軟 化溫度278 °C之中間相瀝青，將熔融之中間相瀝青拉伸， 製造平均直徑13.Ομιη之由碳纖維前驅物構成之前驅物織 物。以金屬刷捕集模嘴正下方之碳纖維前驅物，確認其平 均纖維長度爲8.4cm。 φ (不融化） 接著在空氣氛圍中，於30分鐘內使前驅物織物自200 °C升溫至290°C，製造由不融化碳纖維構成之不融化織物 。不融化碳纖維之氧加成量爲6.5重量％。又，不融化纖 維之平均纖維長度爲8.5cm。 (燒成） 接著在不融化處理時之織物之輸送速度VI與燒成處 理時之織物之輸送速度V2之比VI/V2作爲1.00，連續在 -39- 201009146 氮氣氛圍中於80(TC下進行燒成處理，獲得由碳纖維組成 之不織布，但確認由於織物之收縮導致由碳纖維構成之不 織布切斷。碳纖維之平均纖維徑爲12.Ιμιη，纖維徑之CV 値爲10.2%。又，瀝青系碳纖維之平均纖維長度爲7.3cm ，纖維長度維持率爲86%。而且，測定由瀝青系碳纖維組 成之不織布之拉伸延伸強度爲6.7N/5 cm片。 又，使所得不融化織物在氬氣氣體氛圍中，於I小時 內自室溫燒成至1,500 °C，獲得由瀝青系碳纖維構成之不 織布。評價該瀝青系碳纖維之機械特性後，拉伸延伸度爲 1.2%，拉伸強度爲1.7GPa，拉伸彈性率爲216GPa。 比較例2 (毛氈） 使用彈起高度〇.〇5mm、繭絲數9個、鄰接繭絲間隔 3mm、繭絲深度0.25mm之針，在刺扎數20次/cm2、針深 度10mm下對由比較例1獲得之碳纖維組成之不織布進行 針扎處理獲得毛氈。所得毛氈之層間剝離強度爲 @ 0.15N/5cm片，平均纖維徑爲12·1μπι，基重量爲218g/m2 。爲了製造隔熱材，嘗試將所得毛氈浸漬於酚樹脂（群榮 化學（股）製造，PL-4222，黏度〇.5Pa. s)中，但由於 強度不足而造成毛氈破裂。 比較例3 (紡絲） 在328 °C下，使用由直徑0.2mm φ、長度2mm之毛細 -40- 201009146 管構成之模嘴，自毛細管橫向之狹長口將 之335 °C空氣吹送至由芳香族烴構成之中間 化溫度278 °C之中間相瀝青，將熔融之中技 製造平均直徑21.5 μηι之由碳纖維前驅物 物。以金屬刷捕集模嘴正下方之碳纖維前馬 均纖維長度爲30 _ 4 cm。 φ (不融化） 接著在空氣氛圍中，於30分鐘內使前,1 °C升溫至340°C，獲得由不融化碳纖維構成 。不融化碳纖維之氧加成量爲6.6重量％。 融化纖維之平均纖維長度爲30.5cm。 (燒成） 接著在不融化處理時之織物之輸送速度 # 理時之織物之輸送速度V2之比V1/V2作爲 氮氣氛圍中於800°C下進行燒成處理，獲得 之不織布，但確認由於織物之收縮導致由碳 織布切斷。碳纖維之平均纖維徑爲20.5μιη 値爲9.2%。又，碳纖維之平均纖維長度爲 長度維持率爲8 5 %。又，測定由碳纖維組成 伸延伸強度爲8.4N/5cm片。 又，使所得不融化織物在氬氣氣體氛圍 內自室溫燒成至1,500 °C，獲得由碳纖維構 每分鐘 3,000m 相率1 0 0 %、軟 1相瀝青拉伸， I成之前驅物織 〖物，確認其平 物織物自2 0 0 之不融化織物 又，瀝青系不 VI與燒成處 1.00，連續在 由碳纖維組成 i纖維構成之不 ，纖維徑之CV 25.9cm，纖維 :之不織布之拉 中，於1小時 成之不織布。 -41 - 201009146 評價該碳纖維之機械特性後，拉伸延伸度爲1 .3%，拉伸 強度爲1.6GPa，拉伸彈性率爲23 5 GPa。 比較例4 (紡絲） 在295 下，使用由直徑0.2 mm φ 、長度2 mm之毛細 管構成之模嘴，自毛細管橫向之狹長口將每分鐘5,000m 之3 05 °C空氣吹送至由芳香族烴構成之中間相率〇%、軟化 參 溫度25 8 °C之等向性瀝青，將熔融瀝青拉伸，製造平均直 徑13.5 μπι之由碳纖維前驅物構成之前驅物織物。以金屬 刷捕集模嘴正下方之碳纖維前驅物，確認其平均纖維長度 爲 1 7 · 4cm。 (不融化）Example 6 Q (spinning) At 331 ° C, a nozzle made of a capillary having a diameter of 2 mm in length was used to blow 8,000 m of 3 36 ° C air per minute from the narrow slit of the capillary lateral direction to the aromatic The intermediate phase ratio of the hydrocarbon composition is 100% and the softening temperature is 278. (: mesophase pitch 'stretched the melted mesophase pitch to make a fabric with an average diameter of 1 1.0 μ®. The carbon fiber precursor immediately below the nozzle was collected with a metal brush to confirm its average fiber length of 15.3 cm» -34- 201009146 (without melting) Next, the fabric of the precursor was heated from 200 ° C to 34 (TC in an air atmosphere to produce a non-melting fabric composed of non-melting fibers in 30 minutes. In addition, the average fiber length of the non-melting fiber was 15.2 cm. (Calcination) Next, the baking treatment was continuously performed at 800 ° C in a nitrogen atmosphere to produce a nonwoven fabric composed of carbon fibers. The ratio V1/V2 of the conveying speed VI of the fabric at the time of the non-melting treatment to the conveying speed V2 of the fabric during the baking treatment was 1.02. The average fiber diameter of the obtained carbon fiber was 10.3 μm, and the CV 纤维 of the fiber diameter was 8.2%. The average fiber length of the carbon fiber was 14.2 cm, and the fiber length retention rate was 93%. Moreover, the tensile elongation of the non-woven fabric composed of carbon fibers was measured to be 14 · 6 Ν / 5 cm. In addition, the resulting non-melting fabric was obtained. In an argon gas atmosphere, it was fired from room temperature to 1,500 ° C in an atmosphere of 1 hour to obtain a non-woven fabric composed of carbon fibers. After evaluating the mechanical properties of the carbon fiber, the tensile elongation was 1.55%, and the tensile strength was 1.55%. The tensile modulus is 3.1 5 GPa. Example 7 (felt) The use of a height of 弹.〇4 mm, a number of filatures, a spacing of 3 mm adjacent to the crepe, and a depth of 0.20 mm of the crepe are used in the thorn. The non-woven fabric composed of the carbon fibers obtained in Example 6 was subjected to a needle-bonding treatment to obtain a felt at a number of times of 25 times/cm 2 and a needle depth of 10 mm. The interlayer peeling strength of the obtained felt was -35-201009146 0.48 N/5 cm pieces, and the average fiber diameter was 1〇·5μιη, base weight: 3 90g/m2 Example 8 (Composite to heat-insulating material) The felt produced in Example 7 was immersed in phenol resin (manufactured by Qun Rong Chemical Co., Ltd., PL-2211, viscosity O) In .lPa·s), the excess phenol resin is compressed by a roll press, and then a composite is formed at 25 ° C, and fired at 800 ° C. Then, heat treatment is performed at 2,000 ° C to obtain a content. Carbon fiber insulation material containing 400 parts by weight of carbon relative to 1 part by weight of felt No gap was observed after observing the cross section of the fired body. The tensile strength of the heat insulating material was 〇.79 MPa, and the thermal conductivity was 0.049 W/m·K. After treatment at 2,000 ° C for 20 hours at an oxygen concentration of 20 ppm Tensile strength was 0.76 MPa ° Example 9 (graphitized felt) The felt produced in Example 7 was fired from @ room temperature to 2,500 ° C in 3 hours under an argon atmosphere to obtain a graphitized felt. . The basis weight was 3 8 5 g/m 2 , and the average fiber diameter of the monofilament constituting the graphitized felt was 9.8 μηη. Further, the graphitized felt was heated in air at a temperature of 3 ° C / min from room temperature to 700 ° C and the weight at 700 ° C was reduced to 3.8 wt % of the initial weight. Example 1 0 (spinning) At 336 ° C, a nozzle composed of a capillary of 〇.2ιηιηφ having a diameter of 2 mm and a capillary of -36 to 201009146 was used, and a narrow opening from the lateral direction of the capillary would be 5,000 m per minute 3 3 9 t air is blown to mesophase pitch composed of aromatic hydrocarbons with an intermediate phase ratio of 1 〇〇% and a softening temperature of 278 °C, and the molten mesophase pitch is stretched to produce a precursor of carbon fiber precursors having an average diameter of 15.1 μηη. Fabric. The carbon fiber precursor directly under the nozzle was trapped with a metal brush to confirm that the average fiber length was l〇.4 cm. (No melting) Next, the precursor fabric was heated from 200 ° C to 340 ° C in an air atmosphere for 30 minutes to produce a non-melting fabric composed of non-melting fibers. The oxygen addition amount of the non-melted fiber was 8.4% by weight. Further, the average fiber length of the non-melted fiber was 10.4 cm. (Calcination) Next, the firing treatment was continuously performed at 800 t in a nitrogen atmosphere to produce a non-woven fabric composed of carbon fibers. At this time, the ratio V1/V2 of the conveying speed VI of the fabric at the time of the non-melting treatment to the conveying speed V2 of the fabric during the baking treatment was 1.04. The carbon fiber had an average fiber diameter of 14.3 μm and a fiber diameter of CV 10 of 10.5%. Further, the carbon fiber had an average fiber length of 9.5 cm and a fiber length maintenance ratio of 91%. Further, the tensile elongation of the non-woven fabric composed of carbon fibers was measured to be 15.6 N/5 cm. Further, the non-woven fabric composed of the non-melting fibers was fired from room temperature to 1,500 °C in an argon gas atmosphere for 1 hour to obtain a nonwoven fabric composed of carbon fibers. After evaluating the mechanical properties of the carbon fiber, the tensile elongation was 1.48%, the tensile strength was -37 - 201009146 2.6 GPa, and the tensile modulus was 25 3 GPa. Example 1 1 (Ranunculus) The use of a bounce height of 0 · 0 5 mm, a number of twisted wires of 9, a spacing of 3 mm adjacent to the silk, and a depth of the twisted wire of 〇 · 30 mm '3 times in the number of pricks / The nonwoven fabric composed of the carbon fibers obtained in Example 1 was subjected to a needle-punching treatment to obtain a felt at a depth of cm 2 and a needle depth of 10 mm. The interlaminar peel strength of the obtained felt was 0.39 N/5 cm piece, the average fiber diameter was 14.3 μm, and the basis weight was 460 g/m 2 . Example 12 (Composite to heat insulating material) The felt produced in Example 11 was immersed in a phenol resin. (Manufactured by Qunrong Chemical Co., Ltd., PL-4222, viscosity 0.5Pa. s), after extruding excess phenol resin by roller press, it forms a composite at 250 °C at 8 °C. Boiled under. Subsequently, heat treatment was carried out at 2,000 ° C to obtain a heat insulating material containing carbon fibers. 400 Q parts by weight of carbide is contained with respect to 100 parts by weight of the carbon fiber felt. No void was observed after observing the cross section of the fired body. The tensile strength of the heat insulating material was 0_83 MPa, and the thermal conductivity was 0.049 W/m.K. Tensile strength after treatment at 2,000 ° C and an oxygen concentration of 20 ppm for 24 hours was 0.78 MPa ° Example 13 (graphitized felt) The felt produced in Example 11 was fired from room temperature in 3 hours under an argon atmosphere. At 3,000 ° C, a graphitized felt is obtained. The basis weight is -38 - 201009146 452g/m2, and the average fiber diameter of the monofilament constituting the graphitized hair is 13·8 μηι. Further, the graphitized felt was heated in air at room temperature from 3 ° C / min to 7 Torr. (: The weight loss at 7 ° C is 3. lwt% of the initial weight. Comparative Example 1 (spinning) φ at 335. (:, using a hair system of diameter 〇.2ιηπιφ, length 2 mm The nozzle formed by the tube is blown from the 338 m of 339 ° C per minute to the mesophase pitch composed of aromatic hydrocarbons with an intermediate phase ratio of iOO% and a softening temperature of 278 °C from the narrow mouth of the capillary. The phase asphalt was stretched to produce a precursor fabric composed of a carbon fiber precursor having an average diameter of 13. Ομιη. The carbon fiber precursor immediately below the nozzle was captured by a metal brush, and the average fiber length was confirmed to be 8.4 cm. φ (not melted) Then, the precursor fabric was heated from 200 ° C to 290 ° C in an air atmosphere for 30 minutes to produce a non-melting fabric composed of non-melting carbon fibers. The oxygen addition amount of the non-melting carbon fibers was 6.5% by weight. The average fiber length of the non-melting fiber was 8.5 cm. (Burning) The ratio of the conveying speed VI of the fabric at the time of the non-melting treatment to the conveying speed V2 of the fabric at the time of the baking treatment was 1.00, which was continuously at -39. - 201009146 in a nitrogen atmosphere 80 (The firing treatment was carried out under TC to obtain a non-woven fabric composed of carbon fibers, but it was confirmed that the nonwoven fabric composed of carbon fibers was cut due to shrinkage of the fabric. The average fiber diameter of the carbon fibers was 12. Ι μιη, and the fiber diameter CV 値 was 10.2%. Further, the average carbon fiber length of the pitch-based carbon fiber was 7.3 cm, and the fiber length retention rate was 86%. Further, the tensile elongation of the non-woven fabric composed of the pitch-based carbon fiber was measured to be 6.7 N/5 cm. The woven fabric was fired from room temperature to 1,500 ° C in an argon atmosphere to obtain a non-woven fabric composed of pitch-based carbon fibers. After evaluating the mechanical properties of the pitch-based carbon fibers, the tensile elongation was 1.2%, and the stretching was performed. The strength was 1.7 GPa, and the tensile modulus was 216 GPa. Comparative Example 2 (Felt) A needle having a height of 〇.〇5 mm, a number of filatures, a spacing of 3 mm adjacent to the filature, and a 0.25 mm depth of the crepe was used for puncturing. The non-woven fabric composed of the carbon fibers obtained in Comparative Example 1 was needle-treated to obtain a felt at a number of 20 times/cm 2 and a needle depth of 10 mm. The interlaminar peel strength of the obtained felt was @ 0.15 N/5 cm, and the average fiber diameter was 12· 1μπι, the basis weight is 218g/m2. In order to manufacture the heat insulating material, the obtained felt is immersed in phenol resin (manufactured by Qun Rong Chemical Co., Ltd., PL-4222, viscosity 〇.5Pa.s), but due to insufficient strength. Causes the felt to rupture. Comparative Example 3 (spinning) At 328 °C, a nozzle consisting of a capillary of 40 mm diameter φ and a length of 2 mm was used, and the nozzle was made of 335 ° C from the narrow opening of the capillary. The intermediate phase pitch, which is composed of an aromatic hydrocarbon and having an intermediate temperature of 278 ° C, is melted to produce a carbon fiber precursor having an average diameter of 21.5 μm. The carbon fiber front horse fiber length directly under the metal brush is 30 _ 4 cm. φ (not melted) Next, in an air atmosphere, the temperature was raised to 340 ° C at 1 ° C in 30 minutes to obtain a carbon fiber which was not melted. The oxygen addition amount of the non-melting carbon fiber was 6.6% by weight. The average fiber length of the melted fibers was 30.5 cm. (Calcination) Next, the ratio of the conveyance speed of the fabric at the time of the non-melting treatment, the ratio V1 of the conveyance speed of the fabric V2, V1/V2, was subjected to a calcination treatment at 800 ° C in a nitrogen atmosphere, and the nonwoven fabric was obtained, but it was confirmed that The shrinkage of the fabric results in cutting by the carbon woven fabric. The average fiber diameter of the carbon fibers was 20.5 μmη 値 9.2%. Further, the average fiber length of the carbon fibers was maintained at a rate of 85 %. Further, the tensile strength of the carbon fiber was measured to be 8.4 N/5 cm. Further, the obtained non-melting fabric was fired from room temperature to 1,500 ° C in an argon gas atmosphere to obtain a carbon fiber structure of 3,000 m per minute, a phase ratio of 100%, and a soft 1-phase pitch was stretched, and the I-formed precursor was woven. 〖, confirm that the flat fabric is not melted from the fabric of 200, the asphalt is not VI and the firing point is 1.00, and the i fiber composed of carbon fiber is continuously formed. The fiber diameter is CV 25.9cm, and the fiber is non-woven. In the pull, it is not woven in 1 hour. -41 - 201009146 After evaluating the mechanical properties of the carbon fiber, the tensile elongation was 1.3%, the tensile strength was 1.6 GPa, and the tensile modulus was 23 5 GPa. Comparative Example 4 (spinning) At 295, a nozzle made of a capillary having a diameter of 0.2 mm φ and a length of 2 mm was used, and 5,000 m of 3 05 ° C air per minute was blown from the narrow slit of the capillary to the aromatic An isotropic pitch composed of a hydrocarbon having an intermediate phase ratio of 〇% and a softening temperature of 25 8 ° C was stretched to produce a precursor fabric composed of a carbon fiber precursor having an average diameter of 13.5 μm. The carbon fiber precursor directly under the nozzle was trapped with a metal brush to confirm that the average fiber length was 1 7 · 4 cm. (not melting)
接著在空氣氛圍中，於40分鐘內使前驅物織物自200 °C升溫至320°C，獲得由不融化碳纖維構成之不融化織物 G 。不融化碳纖維之氧加成量爲8.6重量％。又，不融化纖 維之平均纖維長度爲17.5cm。 (燒成） 接著連續在氮氣氛圍中，於800 °C下進行燒成處理， 製造由碳纖維構成之不織布。此時，不融化處理時之織物 之輸送速度VI與燒成處理時之織物之輸送速度V2之比 V1/V2作爲1.〇〇。碳纖維之平均纖維徑爲12.5μιη，纖維 -42- 201009146 徑之cv値爲11.2%。又，碳纖維之平均纖維長度爲 16.9cm，纖維長度維持率爲96.6%。而且，測定由碳纖維 組成之不織布之拉伸延伸強度爲9.5N/5 cm片。 另外，使所得不融化織物在氬氣氣體氛圍中，於1小 時內自室溫燒成至1,5 0(TC，獲得由碳纖維構成之不織布 。評價該碳纖維之機械特性後，拉伸延伸度爲2.2%，拉 伸強度爲〇.7GPa，拉伸彈性率爲29GPa。 比較例5 在氬氣氛圍中，將實施例1製造之由不融化碳纖維構 成之不融化織物於2小時內自室溫燒成至2,300 °C，獲得 由碳纖維構成之不織布。評價該碳纖維之機械特性後，拉 伸延伸度爲0.63%，拉伸強度爲2.4GPa，拉伸彈性率爲 51OGPa。 φ [發明之效果] 本發明之不織布由於含有高延伸度及高彈性率之碳纖 維，而可適於較好地用於機械強度優異之針扎處理之毛氈 化。依據本發明不織布之製造方法，藉由使不融化纖維之 氧加成量在特定範圍之內，可提升瀝青系碳纖維之拉伸延 伸度。本發明之毛氈之機械強度優異，尤其是層間剝離強 度優異。依據本發明毛氈之製造方法，可獲得機械強度優 異，尤其是層間剝離強度優異之毛氈。本發明之隔熱材之 機械強度及隔熱性優異。 -43- 201009146 [產業上利用之可能性] 本發明之不織布、毛氈及隔熱材可利用作爲產業用機 械臂或飛機之構造構件。 【圖式簡單說明】 圖1爲針之繭絲部之模式圖。 圖2爲針之模式圖。 【主要元件符號說明】 1 :繭絲深度 2:彈起（kick up)高度 3 :毛氈 4 :針 5 :針床 6 :距離前端最短距離之繭絲（第1繭絲） 7 :針深度 8 :鄰接繭絲間隔 -44-Next, the precursor fabric was heated from 200 ° C to 320 ° C in an air atmosphere for 40 minutes to obtain an unmelted fabric G composed of non-melting carbon fibers. The oxygen addition amount of the non-melting carbon fiber was 8.6% by weight. Further, the average fiber length of the non-melting fiber was 17.5 cm. (Calcination) Next, the baking treatment was continuously performed at 800 ° C in a nitrogen atmosphere to produce a nonwoven fabric composed of carbon fibers. At this time, the ratio V1/V2 of the conveying speed VI of the fabric at the time of the non-melting treatment to the conveying speed V2 of the fabric during the baking treatment was 1. The average fiber diameter of the carbon fiber was 12.5 μm, and the cv値 of the fiber -42-201009146 was 11.2%. Further, the carbon fiber had an average fiber length of 16.9 cm and a fiber length maintenance ratio of 96.6%. Further, the tensile elongation of the non-woven fabric composed of carbon fibers was measured to be 9.5 N/5 cm. In addition, the obtained non-melting fabric was fired from room temperature to 1,500 in an argon gas atmosphere for 1 hour to obtain a non-woven fabric composed of carbon fibers. After evaluating the mechanical properties of the carbon fiber, the tensile elongation was 2.2%, tensile strength was 〇7 GPa, and tensile modulus was 29 GPa. Comparative Example 5 An unmelted fabric composed of non-melting carbon fibers produced in Example 1 was fired from room temperature in 2 hours under an argon atmosphere. A nonwoven fabric composed of carbon fibers was obtained at 2,300 ° C. After evaluation of the mechanical properties of the carbon fibers, the tensile elongation was 0.63%, the tensile strength was 2.4 GPa, and the tensile modulus was 51 OGPa. φ [Effect of the Invention] The present invention The non-woven fabric is suitable for use in the felting of the needle-punching treatment excellent in mechanical strength because it contains carbon fibers having high elongation and high modulus of elasticity. According to the manufacturing method of the non-woven fabric of the present invention, the oxygen of the non-melting fibers is made The addition amount is within a specific range, and the tensile elongation of the pitch-based carbon fiber can be improved. The felt of the present invention is excellent in mechanical strength, especially excellent in interlayer peel strength. Manufacture of felt according to the present invention According to the method, it is possible to obtain a felt excellent in mechanical strength, in particular, excellent in interlayer peeling strength. The heat insulating material of the present invention is excellent in mechanical strength and heat insulating property. -43- 201009146 [Probability of industrial use] Non-woven fabric, felt of the present invention The heat insulating material can be used as a structural member of an industrial robot arm or an aircraft. [Simplified illustration of the drawing] Fig. 1 is a schematic view of the yarn portion of the needle. Fig. 2 is a schematic diagram of the needle. [Description of main components] 1 : 茧 深度 depth 2: kick up height 3 : felt 4 : needle 5 : needle bed 6 : the shortest distance from the front end of the crepe (the first crepe) 7 : the needle depth 8 : the adjacent crepe spacing - 44 -