TW201118121A - Insulated pitch-based graphitized short fibers - Google Patents

Insulated pitch-based graphitized short fibers Download PDF

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Publication number
TW201118121A
TW201118121A TW99124927A TW99124927A TW201118121A TW 201118121 A TW201118121 A TW 201118121A TW 99124927 A TW99124927 A TW 99124927A TW 99124927 A TW99124927 A TW 99124927A TW 201118121 A TW201118121 A TW 201118121A
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Taiwan
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resin
pitch
graphitized short
based graphitized
short fibers
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TW99124927A
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Chinese (zh)
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Hiroki Sano
Hiroshi Hara
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Teijin Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Fibers (AREA)

Abstract

Disclosed is a thermally conductive material which has insulating properties and excellent thermal conductivity at the same time. Specifically disclosed are insulated pitch-based graphitized short fibers that are characterized by being obtained by coating pitch-based graphitized short fibers with such a resin which does not have a melting point at 250 DEG C or less and the precursor of which is in a liquid state, or with such a resin which or the precursor of which is soluble in at least one kind of solvent.

Description

201118121 六、發明說明： 【發明所屬之技術領域】 本發明關於絕緣化之瀝青系石墨化短纖維，其係藉由 不具有250 °C的熔點’且其前驅物爲液狀，或前驅物或其 本身爲可溶於溶劑中之樹脂，塗覆瀝青系石墨化短纖維， 其可適用於電子機器、電子零件的散熱構件。 【先前技術】 高性能的碳纖維係可分類爲以聚丙烯腈（PAN)當作 原料的PAN系碳纖維及以一列的瀝青類當作原料的瀝青系 碳纖維。而且，碳纖維與通常的合成高分子比較下，利用 強度·彈性模數顯著高的特徵，而廣泛使用於航空.宇宙 用途、建築•土木用途、產業用機器人、運動·休閒用途 等。又，PAN系碳纖維主要多用於利用其強度的領域，而 且瀝青系碳纖維多使用於利用彈性模數的領域。 近年來，省能量所代表的能量之有效率的使用方法係 受到注目，另一方面隨著高速化的CPU或電子電路的焦耳 熱所致的發熱係正在被視爲重大的問題。又，於以電子注 入當作發光原理的電致發光元件中，亦同樣地成爲重大的 問題而明顯存在化。另一方面，若向形成各種元件的製程 看，則要求環境顧慮型製程，作爲其對策，正在更換到沒 有添加鉛的所謂無鉛焊料。無鉛焊料由於熔點比通常的有 鉛焊料高，故要求製程的熱之有效率的使用。而且，爲了 解決如此來自製品•製程所內含的熱之問題，必須達成熱 -5- 201118121 的有效率之處理（熱管理）。 一般地，與其它合成高分子比較下，碳纖維可說是導 熱率高，但是針對熱管理用途，檢討進一步的導熱率之提 高。然而，市售的PAN系碳纖維之導熱率通常比200 W/ ( m • K )還小。此係因爲PAN系碳纖維爲所謂的難石墨化碳纖 維，提高擔負導熱率的石墨性係非常困難。相對於此，瀝 青系碳纖維係稱爲易石墨化碳纖維，與PAN系碳纖維相比 ，由於可提高石墨性，故看到容易達成高導熱率。因此， 連有效率地展現導熱性的形狀都考慮的高導熱性塡料係有 實現的可能性。 其次考察熱管理中所用的成形體之特徵。一般地，碳 纖維顯示導電性。因此，碳纖維與基質所複合成的組成物 係顯示導電性。然而，前述的CPU或電子電路多安裝於絕 緣性的底座等。因此，將用碳纖維的組成物使用於電子底 座係困難。 專利文獻1、2中提案於導熱性組成物上被覆絕緣層之 方法。然而，由於不是對於導熱性塡料的加工，故對應於 複雜的成形體之絕緣處理係困難。又，專利文獻3中提案 由氧化矽所成的絕緣層，專利文獻4中提案以由矽石或碳 化砂所成絕緣層來被覆導熱性塡充材之方法。然而，由無 機化合物所成的絕緣層係脆的，與樹脂的混煉之際被覆會 剝落，絕緣性的維持係困難。其中，碳化矽係硬度高，對 混煉機等有造成傷害之虞。 (專利文獻1)特開2008 -208 3 1 6號公報 201118121 (專利文獻2 )特開2 0 0 8 - 2 0 5 4 5 3號公報 (專利文獻3 )特開2 Ο Ο 7 - 1 2 8 9 8 6號公報 (專利文獻4 )特開2 0 0 7 - 1 0 7 1 5 1號公報 【發明內容】 本發明之目的在於提供一種絕緣化之瀝青系石墨化短 纖維，其在基質中的網絡形成能力優異，兼具高的導熱性 與絕緣性。又，本發明之目的在於提供由絕緣化之瀝青系 石墨化短纖維與由熱塑性樹脂、熱硬化性樹脂及橡膠所成 之群選出的至少1種之基質成分所成的導熱性組成物，以 及由彼等所成的成形體。 解決問題的手段 本發明者們爲了得到顯示高的導熱性且顯示絕緣性之 導熱材’重複專心致力的檢討，結果發現以導熱性優異的 瀝青系石墨化短纖維爲核心，藉由不具有2 5 0 t以下的熔 點’且其前驅物液狀’或前驅物或其本身爲可溶於至少1 種類的溶劑中之樹脂來塗覆，可得到兼具高的導熱性與絕 緣性之導熱材，而達成本發明。 本發明係一種絕緣化之瀝青系石墨化短纖維，其特徵 爲藉由具有250°C以下的熔點，且其前驅物爲液狀，或前 驅物或其本身爲可溶於至少1種類的溶劑中之樹脂，塗覆 表面。 201118121 發明的效果 藉由本發明，可提供兼具高的導熱性與絕緣性的絕緣 化之瀝青系石墨化短纖維，藉此可得到具有絕緣性的導熱 性組成物及其成形體。藉此，對要求高的散熱特性之電子 機器、電子底座等的應用係成爲可能。 【實施方式】 實施發明的最佳形態 以下依順序說明本發明的實施形態。 [絕緣化之瀝青系石墨化短纖維] 本發明的絕緣化之瀝青系石墨化短纖維之特徵爲具有 在表面不具有250°C以下的熔點，且其前驅物爲液狀，或 溶解於溶劑中的樹脂層之瀝青系石墨化短纖維。絕緣化之 瀝青系石墨化短纖維係在表面上具有經由塗覆所成的樹脂 層。以將石墨化短纖維絕緣爲目的，石墨化短纖維的表面 較佳爲幾乎完全被樹脂層所被覆。 瀝青系石墨化短纖維的比電阻爲1〇_4Ω · cm等級，顯示 導電性。又，即使與樹脂混合而成爲成形品時，其成形品 也顯示導電性。因此，使用於如密封劑之導電性不宜的部 分之熱對策係困難。相對於其，一般的樹脂係超過1014Ω. cm的等級，顯示高的絕緣性。因此，藉由以樹脂塗佈瀝青 系石墨化短纖維的每一條，可謀求瀝青系石墨化短纖維的 絕緣化。然而，樹脂一般爲導熱性大幅比瀝青系石墨化短 201118121 纖維差。因此，於藉由樹脂將瀝青系石墨化短纖維絕緣化 之際’必須以少量的樹脂進行塗覆。因此，要求樹脂前驅 物或溶解有樹脂的溶液係成爲液狀。此係因爲若塗覆劑爲 液狀，則可將樹脂層均勻地塗覆在瀝青系石墨化短纖維上 ’可抑制樹脂的量。 本發明的絕緣化之瀝青系石墨化短纖維之比電阻較佳 爲1.0xl〇6D.cm以上。比電阻若未達l_0xl06Q.cm，則對成 形品的比電阻，無法期待可賦予高的電阻。再者，絕緣化 之瀝青系石墨化短纖維之比電阻的實質上限係1.0x1 〇Ι4Ω. cm ° 本發明的絕緣化之瀝青系石墨化短纖維，較佳爲在表 面上形成有均勻的絕緣層之瀝青系石墨化短纖維，即在掃 描型電子顯微鏡的觀察表面係實質上平坦。所謂的實質上 平坦，就是在掃描型電子顯微鏡中以800〜1000倍所觀察 的影像之觀察視野中，1條的瀝青系石墨化短纖維中的凹 凸及缺陷係10個地方以下，或在以2000倍所觀察的影像之 觀察視野中，每1條的凹凸及缺陷係1 5個地方以下。此處 所謂的凹凸，就是意味以掃描型電子顯微鏡進行觀察之際 ，絕緣化之瀝青系石墨化短纖維的表面，即塗佈面上有劇 烈的凹凸，具體地有高度或深度3 μιη以上的凹凸。所謂的 缺陷，就是意味以掃描型電子顯微鏡進行觀察之際，觀察 到在絕緣化之瀝青系石墨化短纖維的一部分上沒有塗佈樹 脂，瀝青系石墨化短纖維的表面之一部分露出。 本發明的絕緣化之瀝青系石墨化短纖維，較佳爲相對 -9 - 201118121 於100重量份的該瀝青系石墨化短纖維而言，所塗覆的樹 脂之存在係1〜10重量份。所塗覆的樹脂之存在若爲1重量 份以下，則不能充分塗覆瀝青系石墨化短纖維，無法期待 絕緣性。相反地，所塗覆的樹脂之存在若爲1 0重量份以上 ，則塗覆瀝青系石墨化短纖維的樹脂係過多，於成爲成形 品之際，得到高的導熱性係易變困難。相對於1 00重量份 的瀝青系石墨化短纖維而言，較佳爲3〜7重量份，更佳爲 3〜5重量份。 [塗覆的樹脂] 作爲塗覆瀝青系石墨化短纖維的樹脂所要求的特性， 可舉出不具有25 0°C以下的熔點。使用熱塑性樹脂當作基 質時’在基質的熔點以上之溫度進行混煉的情況係多。當 所塗覆的樹脂之熔點未達基質的熔點時，由於所塗覆的樹 脂被熔解、去除，故難以維持絕緣性。因此，要求在許多 熱塑性樹脂的熔點以上的不具有2 5 0 °C以下之熔點。所謂 之不具有250 °C以下的熔點，就是指熔點超過250 °C，或不 具有熔點本身。更佳爲不具有3 0 0 °C以下的熔點。熔點係 可藉由差示掃描熱量計等來測定。 又’從可塗覆瀝青系石墨化短纖維且可在瀝青系石墨 化短纖維的表面固定化之觀點來看，用於塗覆的樹脂係要 求前驅物爲液狀，或前驅物或其本身可溶於至少1種類的 溶劑中。此處所謂的可溶於溶劑中，具體地就是指相對於 100重量份的溶劑而言’可將0_1〜10重量份的前驅物或樹 -10- 201118121 脂在20°C〜低於溶劑的沸點1 〇t的溫度之條件下溶解。 作爲所塗覆的樹脂，只要滿足不具有25 〇〇c的熔點， 且其前驅物爲液狀’或前驅物或其本身爲可溶於至少I種 類的溶劑中之要件，則沒有特別的限定，較佳可舉出熱硬 化性樹脂或芳香族聚醯胺、芳香族聚醯亞胺 '脂肪族聚醯 亞胺。 熱硬化性樹脂係沒有特別的限定，具體地可舉出環氧 樹脂、熱硬化性丙烯酸樹脂、胺基甲酸乙酯樹脂、聚矽氧 樹脂。其中，環氧樹脂係與瀝青系石墨化短纖維的親和性 特別優異’瀝青系石墨化短纖維與樹脂的接著力高，即使 於混合以樹脂所絕緣化的瀝青系石墨化短纖維與基質而製 作成形體之際’絕緣用樹脂也不易由瀝青系石墨化短纖維 剝離，有可維持高絕緣性的傾向。 環氧樹脂係沒有特別的限定，可爲混合硬化前的樹脂 之主劑與硬化劑而使進行熱硬化反應者。作爲主劑，有脂 肪族系環氧樹脂、含雙酚等的芳香族系環氧樹脂等。又， 作爲硬化劑，有胺系硬化劑、酸酐系硬化劑。再者，按照 需要，亦可使用硬化觸媒。作爲硬化觸媒，有咪唑系硬化 觸媒等。此等主劑、硬化劑、硬化觸媒成分係可按照需要 而適宜混合使用。 芳香族聚醯胺係沒有特別的限定，具體地可例示來自 由對苯二甲酸及/或間苯二甲酸所成的芳香族二羧酸成分 、與由1，4-苯二胺、1,3-苯二胺、3,4，-胺基二苯基醚、 4,4’·二胺基二苯基醚及1，3-雙（3-胺基苯氧基）苯所成之 -11 - 201118121 群選出的至少一種之芳香族二胺成分的全芳香族聚醯胺' 及芳香族聚醯胺醯亞胺類及其共聚物。 芳香族聚醯亞胺係沒有特別的限定，具體地可例示由 苯均四酸酐等所成的芳香族四羧酸二酐、與由4，4-二胺基 二苯基醚等所成的芳香族二胺之聚合物。 脂肪族聚醯亞胺係沒有特別的限定，具體地可例示由 飽和脂環式四羧酸二酐、及/或雙環（2,2,2 )-辛-7-烯-2,3,5,6-四羧酸二酐、及/或5-(2,5-二氧代-四糠基）-3-甲 基-4-環己烯-1，2-二羧酸酐所成之群選出的至少一種之脂 肪族四羧酸二酐、與由1，3·雙（3-胺基甲基）環己烷、 4，4’-二胺基·二環己基-甲烷、雙（2-胺基乙氧基）乙烷' N，N-雙（3-胺基丙基）甲基胺、乙二胺所成之群選出的至 少一種之脂肪族二胺的聚合物。 芳香族聚醯胺、芳香族聚醯亞胺、脂肪族聚醯亞胺在 不損失其特性的範圍內，亦可爲共聚物。 [樹脂的塗覆方法] 樹脂的塗覆方法係沒有特別的限定，具體地可舉出（ 1)調製絕緣溶液，供用於塗覆之方法，或（2)不用溶劑 的氣體處理法等。 (1)的絕緣溶液係液狀的前驅物、於液狀的前驅物 中更按照需要混合有溶劑者、或前驅物或樹脂溶於溶劑中 者。 作爲構成絕緣溶液的具體較佳溶劑，於環氧樹脂的情 -12- 201118121 況，雖然對於硬化前的樹脂之主劑與硬化劑之混合液 更使用溶劑，但較佳可舉出丙酮、甲苯、甲基乙基酮 基異丁基酮。於聚矽氧樹脂的情況中亦同樣地，雖然 硬化前的樹脂之主劑與硬化劑之混合液中會更使用溶 但較佳可舉出甲苯、己烷。於芳香族聚醯胺的情況， 出溶解其的n，n-甲基吡咯烷酮、二甲基乙醯胺、二甲 醯胺。於芳香族聚醯亞胺的情況，可舉出前驅物可 N，N-甲基吡咯烷酮。於脂肪族聚醯亞胺的情況，可舉 驅物可溶的Ν,Ν-甲基吡咯烷酮。 作爲（1 )的具體方法，於熱硬化性樹脂、芳香 醯亞胺或脂肪族聚醯亞胺的情況，可舉出添加前驅物 需要更添加溶劑而得到絕緣溶液，於其中混合瀝青系 化短纖維，以噴霧、過濾等的手法來塗覆必要的絕緣 後，進行熱處理而使樹脂硬化之手法。於芳香族聚醯 情況，可舉出將其溶於溶劑中而得到絕緣溶液，於其 合瀝青系石墨化短纖維，以噴霧、過濾等的手法來塗 要的絕緣溶液後，藉由乾燥來去除溶劑之方法。 作爲（2)的氣體處理法，具體地可舉出在瀝青 墨化短纖維上使樹脂的原料化合物之氣體聚合而塗覆 法。再者，於氣體處理法中，爲了使在瀝青系石墨化 維上進行反應，較佳爲對瀝青系石墨化短纖維施予表 理。 由於對於1 〇〇重量份的如上述之瀝青系石墨化短 而言，塗覆樹脂量較佳爲1〜1 〇重量份，故於（1 )的 中會 、甲 對於 劑， 可舉 基甲 溶的 出前 族聚 及視 石墨 溶液 胺的 中混 覆必 系石 之手 短纖 面處 纖維 方法 -13- 201118121 中，在塗覆後較佳爲選擇絕緣溶液量，以使得能確保所欲 的樹脂量。此處，（1)的方法中用於塗覆的絕緣溶液量 若過多，則由於溶液的表面張力等而使溶液及塡料凝聚， 均勻的塗覆變困難。結果，在絕緣層中多發生缺陷，難以 均勻地塗覆塡料全體而達成絕緣化。又，大多數的有機化 合物或無機化合物係導熱性比瀝青系石墨化短纖維差。因 此，於藉由有機化合物或無機化合物將瀝青系石墨化短纖 維絕緣化之際，爲了抑制導熱性的降低，必須儘可能地以 少量來形成絕緣表面。因此，於形成絕緣表面之際，必須 以少量來均句塗覆。絕緣溶液的較佳重量比係相對於1 00 重量份的瀝青系石墨化短纖維而言，樹脂或前驅物爲1〜 10重量份。使用溶劑時，相對於1〇〇重量份的樹脂或前驅 物而言，溶劑爲1000〜20000重量份。 拉開塡料彼此的距離且減少絕緣溶液接觸塡料表面之 量者，係可縮短乾燥時間且抑制凝聚，可達成均句的絕緣 層之塗覆。或，於塗覆絕緣層之際，若如（2)之氣體處 理法而不使用溶液，則可避免凝聚。若考慮生產性，較佳 爲可連續處理的噴霧乾燥法。 [噴霧乾燥法] 噴霧乾燥法係將由絕緣層形成用溶液與瀝青系石墨化 短纖維所成的漿體經由旋轉圓盤或噴嘴噴灑出，放出霧狀 的噴霧。藉由熱風碰撞此噴霧，溶劑幾乎瞬間地乾燥，可 達成瀝青系石墨化短纖維的表面之塗覆。又，於絕緣層中 -14- 201118121 使用熱硬化樹脂時’亦可藉由此熱風進行硬化，可塗覆耐 熱性高的絕緣層。 用於噴霧法的溶液’只要是可分散瀝青系石墨化短纖 維’可使絕緣層形成材料溶解或分散，且可噴霧成霧狀即 可’從揮發性的觀點來看，較佳爲使用沸點爲1 2 0 «C以下 的有機溶劑。 作爲構成噴霧法的溶液之較佳溶劑，係與上述絕緣溶 液的欄中所列舉者相同。 噴霧溶液的較佳重量比，係相對於1 〇〇重量份的瀝青 系石墨化短纖維而言’樹脂或前驅物爲1〜！ 〇重量份，相 對於100重量份的樹脂或前驅物而言，溶劑爲1〇〇〇〜20000 重量份。 [瀝青系石墨化短纖維] 本發明中的瀝青系石墨化短纖維，從塡充時的成形性 或導熱性之展現等的觀點來看，較佳爲使用特定形狀的瀝 青系石墨化短纖維。 本發明中的瀝青系石墨化短纖維以光學顯微鏡所觀測 的平均纖維直徑（D1)較佳爲2〜20μηι。D1低於2μηι時， 由於與樹脂複合之際該短纖維的條數變多，故樹脂/短纖 維混合物的黏度變高，成形會變困難。相反地，D1若超過 2 0 μιη ’則由於與樹脂複合之際短纖維的條數變少，故該短 纖維彼此係難以接觸，作爲複合材時會難以發揮有效果的 導熱率。D1的較佳範圍爲5〜15μιη，更佳爲7〜13μηι。 -15- 201118121 本發明中的瀝青系石墨化短纖維係於以光學顯微鏡所 觀測的瀝青系石墨化短纖維中，纖維直徑分散（S1 )對平 均纖維直徑（D1)之百分率（CV値）較佳爲3〜15%。CV 値係纖維直徑的偏差之指標，愈小則意味製程安定性愈高 ，製品的偏差愈小。當CV値小於3 %時，由於纖維直徑係 極度整齊，進入瀝青系石墨化短纖維的間隙之尺寸小的短 纖維之量係變少，更緻密地塡充瀝青系石墨化短纖維係變 困難，結果會難以得到高性能的複合材。相反地，當CV値 大於15%時，於與樹脂複合之際，分散性變差，得到具有 均一性能的複合材會變困難。CV値較佳爲5〜13%。CV値 係可藉由調節紡絲時的熔融中間相瀝青之黏度而實現，具 體地於以熔體流動法進行紡絲之際，將在紡絲時的噴嘴孔 之熔融黏度調整至5.0〜25.0Pa*S而實現》 瀝青系石墨化短纖維一般有由平均纖維長未達lmm所 成的硏磨纖維與由平均纖維長1mm以上且未達l〇mm所成的 切段纖維之2種類。硏磨纖維的外觀由於是粉狀而分散性 優異，切段纖維的外觀由於接近纖維狀，故有容易得到纖 維彼此的接觸之特徵。 本發明中的瀝青系石墨化短纖維係相當於硏磨纖維， 其平均纖維長（L1)較佳爲20〜500 μιη。此處，平均纖維 長係個數平均纖維長，可於光學顯微鏡下使用測長器，在 複數的視野中測定指定的條數，由其平均値來求得。L 1小 於2 Ομιη時，該短纖維彼此係變難以接觸，難以期待有效果 的導熱率。相反地，大於5〇〇μιη時，與樹脂混合之際，基 μ -16- 201118121 質/短纖維混合物的黏度變高，成形性有變低的傾向。更 佳爲2 0〜3 00 μπι的範圍。得到如此的瀝青系石墨化短纖維 之手法係沒有特別的限制，可藉由調節硏磨的條件，即以 切刀等進行粉碎之際的切刀之旋轉速度、球磨機的旋轉數 、噴射磨機的氣流速度、壓碎機的衝撞次數、硏磨裝置中 的滯留時間，而控制平均纖維長。又，可由硏磨後的瀝青 系碳質短纖維中，藉由筛選等的分級操作，去除短的纖維 長度或長的纖維長度之瀝青系碳質短纖維而調整。 本發明中的瀝青系石墨化短纖維係由石墨結晶所組成 ，來自六角網面的成長方向之雛晶尺寸較佳爲30nm以上。 雛晶尺寸係在六角網面的成長方向中對應於石墨化度者， 爲了展現熱物性，必須爲一定尺寸以上。六角網面的成長 方向之雛晶尺寸係可藉由X射線繞射法來求得。測定手法 爲集中法，解析手法可適用使用學振法。六角網面的成長 方向之雛晶尺寸係可使用來自（1 1 0 )面的繞射線而求得 〇 本發明中的瀝青系石墨化短纖維，較佳爲於透射型電 子顯微鏡的纖維末端觀察中，石墨烯薄片之端面係關閉。 於石墨烯薄片的端面關閉時，不易引起多餘的官能基之發 生、或起因於形狀所致的電子之局部存在化。因此，在瀝 青系石墨化短纖維中不產生活性點，於以樹脂塗覆之際， 由於觸媒活性點的降低而可抑制硬化不良。又，亦可減低 水等的吸附，例如即使與如聚酯之伴隨水解的樹脂之混煉 中，也可帶來顯著的濕熱耐久性能力提高。於以放大50萬 -17- 201118121 〜40 0萬倍的透射型電子顯微鏡之視野範圍中，石墨烯薄 片的端面較佳爲8 0%關閉。此係因爲若爲8 0%以下，則有 引起多餘的官能基之發生、或起因於形狀所致的電子之局 部存在化、促進與其它材料的反應之可能性而不宜。石墨 烯薄片端面的閉鎖率較佳爲9 0 %以上，更佳爲9 5 %以上。 取決於在石墨化之前實施粉碎，或在石墨化的後實施 粉碎，石墨烯薄片端面構造係大不同相。即，於石墨化後 進行粉碎處理時’石墨化所成長的石墨烯薄片係被切斷而 斷裂，石墨烯薄片端面容易成爲打開的狀態。另一方面， 於石墨化前進行粉碎處理時，在石墨的成長過程中，石墨 烯薄片端面係彎曲成U字狀，容易成爲彎曲部分露出瀝青 系石墨化短纖維端部之構造。因此，爲了得到石墨烯薄片 端面閉鎖率超過80%的瀝青系石墨化短纖維，較佳爲在粉 碎後進行石墨化處理。 本發明中的瀝青系石墨化短纖維以掃描型電子顯微鏡 觀察的側面之表面較佳爲實質上平坦。此處，所謂之實質 上平坦，就是意味在瀝青系石墨化短纖維不具有如原纖維 (fibril )構造之劇烈凹凸。於瀝青系石墨化短纖維的表 面上有如劇烈的凹凸之缺陷存在時，在基質樹脂的混煉之 際，隨著表面積的增大，引起黏度的增大，而使成形性變 差。因此，如表面凹凸之缺陷係宜爲儘可能小的狀態。更 具體地，於掃描型電子顯微鏡中以1 000倍所觀察的影像之 觀察視野中，如凹凸的缺陷係10個地方以下。於以2000倍 所觀察的影像之觀察視野中，每1條的凹凸及缺陷係15個 -18- 201118121 地方以下。 作爲得到如此的瀝青系石墨化短纖維之手法，較佳爲 可在進行硏磨後實施石墨化處理而得者。 以下說明本發明所用的瀝青系碳質短纖維之較佳製造 法。 作爲本發明所用的瀝青系碳質短纖維之原料，例如可 舉出萘或菲等的縮合多環烴化合物、石油系瀝青或煤系瀝 青等的縮合雜環化合物等。其中，較佳爲萘或菲等的縮合 多環烴化合物，特佳爲中間相瀝青。中間相瀝青的中間相 率較佳爲至少90%以上，尤佳爲95%以上，更佳爲99%以上 。再者，中間相瀝青的中間相率係可用偏光顯微鏡來觀察 熔融狀態的瀝青而確認。 再者，原料瀝青的軟化點較佳爲2 3 0 °C以上3 4 0 °C以下 。不熔化處理必須在比軟化點還低的溫度處理。因此，軟 化點若低於2 3 0°C，則至少必須在未達軟化點的低溫度進 行不熔化處理，結果不熔化係需要長時間而不宜。另一方 面，軟化點若超過340°C，則在紡絲中必須超過34CTC的高 溫，由於發生引起瀝青的熱分解，所產生的氣體在絲中產 生氣泡的等之問題而不宜。軟化點的尤佳範圍爲2 5 0°C以 上3 20°C以下，更佳爲260°C以上310°C以下。再者，原料瀝 青的軟化點係可藉由曼特拉（Mettler )法來求得。原料瀝 青亦可適宜組合二種以上而使用。較佳爲所組合的原料瀝 青之中間相率係至少90 %以上，軟化點係2 3 0 °C以上34〇°C 以下。 -19- 201118121 中間相瀝青係藉由熔融法紡絲，然後藉由不熔化、碳 化、粉碎、石墨化而成爲瀝青系石墨化短纖維。視情況而 定，於粉碎之後，亦有導入分級步驟。 以下各步驟說明較佳的態樣。 於紡絲方法中，沒有特別的限制，可適應熔融紡絲法 。具體地，可舉出以捲繞機來牽引由噴嘴所吐出的中間相 瀝青之通常紡絲延伸法，使用熱風當作霧化（atomizing) 源的熔體流動法，利用離心力來牽引中間相瀝青的離心紡 絲法等。其中，基於瀝青系碳纖維前驅物的形態之控制、 生產性的提高等之理由，宜使用熔體流動法。因此，以下 關於本發明的瀝青系石墨化短纖維之製造方法，記載熔體 流動法。 形成瀝青系碳纖維前驅物的紡絲噴嘴之形狀亦可爲任 何樣式。通常使用真圓狀者，適時使用橢圓等的異型形狀 之噴嘴亦毫無問題。噴嘴孔的長度（LN )與孔徑（DN ) 之比（LN/DN )較佳爲2〜20的範圍。LN/DN若超過20，則 對通過噴嘴的中間相瀝青給予強的剪切力，在纖維截面中 展現輻射狀構造。輻射狀構造的展現由於會在石墨化的過 程中使在纖維截面產生裂紋，引起機械特性的降低而不宜 。另一方面，LN/DN若未達2，則無法對原料瀝青給予剪 切，結果成爲石墨的配向低之瀝青系碳纖維前驅物。因此 ，即使石墨化也無法充分提高石墨化度，難以提高導熱性 而不宜。爲了達成機械強度與導熱性的並存，必須對中間 相瀝青給予適度的剪切。因此，噴嘴孔的長度（LN)與孔 -20- 201118121 徑（DN)之比（LN/DN)較佳爲2〜20的範圍，更且特佳 爲3〜1 2的範圍。 紡絲時的噴嘴之溫度、中間相瀝青係與通過噴嘴之際 的剪切速度、由噴嘴所吹出的風量、風的溫度等有關，而 沒有特別的限制，只要是可維持安定的紡絲狀態之條件即 可，即中間相瀝青在噴嘴孔的熔融黏度爲在1〜l〇〇Pa· S之 範圍。 通過噴嘴的中間相瀝青之熔融黏度未達lPa_s時，熔 融黏度過低，無法維持絲形狀而不宜。另一方面，中間相 瀝青的熔融黏度超過loop a· S時，由於對中間相瀝青給予 強的剪切力，在纖維截面形成輻射狀構造而不宜。爲了使 對中間相瀝青所給予的剪切力在適當之範圍，而且維持纖 維形狀’必須控制通過噴嘴的中間相瀝青之熔融黏度。因 此，中間相瀝青的熔融黏度較佳爲在1〜1 〇 〇 p a . s之範圍， 尤佳爲在3〜30Pa.s之範圍，更佳爲在5〜25Pa.s之範圍。 本發明所用的瀝青系石墨化短纖維較佳係平均纖維直 徑（D1 )爲2〜20μιη以下，瀝青系石墨化短纖維的平均纖 維直徑之控制係可藉由變更噴嘴的孔徑，或變更來自噴嘴 的原料瀝青之吐出量’或變更牽伸比來調整。牽伸比的變 更係可藉由將經加溫到100〜400 t的每分鐘1〇〇〜2 〇〇〇 〇m 之線速度的氣體噴吹到細化點附近而達成。所噴吹的氣體 係沒有特別的限制’從成本效能與安全性的方面來看，宜 爲空氣。 灑青系碳纖維前驅物係被補集在金屬網等的帶上而成 -21 - 201118121 爲瀝青系碳纖維前驅物網布（web)。那時，可藉由帶搬 送速度來調整任意的單位面積重量，視需要亦可藉由交叉 鋪網等的方法使層合。考慮生產性及製程安定性，瀝青系 碳纖維前驅物網布的單位面積重量較佳爲150〜1 000g/m2 〇 如此所得之瀝青系碳纖維前驅物網布係可藉由眾所周 知的方法進行不熔化處理，而成爲瀝青系不熔化纖維網布 。不熔化係可在使用空氣或於空氣中加有臭氧、二氧化氮 、氮、氧、碘、溴的氣體之氧化性環境下實施，若考慮安 全性、便利性，則宜在空氣中實施。又，以分批處理、連 續處理中任一者皆可處理，但若考慮生產性，則宜爲連續 處理。不熔化處理係可藉由在150〜350 °C的溫度，給予一 定時間的熱處理而達成。更佳的溫度範圍爲160〜340 °C。 升溫速度適宜使用1〜10°C/分鐘，連續處理時藉由依順序 通過設定在任意溫度的複數之反應室，可達成上述升溫速 度。考慮生產性及製程安定性，升溫速度的較佳範圍係3 〜9°C/分鐘。 瀝青系不熔化纖維網布係在600〜2000°C的溫度，於 真空中或在使用氮、氬、氪等的惰性氣體之非氧化性環境 中被碳化處理，而成爲瀝青系碳纖維網布。考慮成本面， 碳化處理宜爲在常壓且氮環境下之處理。又，以分批處理 、連續處理中任一者皆可處理，但若考慮生產性，則宜爲 連續處理。 經碳化處理的瀝青系碳纖維網布，爲了成爲所欲的纖201118121 VI. Description of the Invention: [Technical Field] The present invention relates to an insulated pitch-based graphitized short fiber which has a melting point of 250 ° C and whose precursor is liquid, or a precursor or The resin itself is a resin soluble in a solvent, and is coated with a bituminized graphitized short fiber, which is applicable to a heat dissipating member of an electronic device or an electronic component. [Prior Art] High-performance carbon fibers can be classified into PAN-based carbon fibers using polyacrylonitrile (PAN) as a raw material and pitch-based carbon fibers using a row of pitch as a raw material. In addition, carbon fibers are widely used in aerospace, space applications, construction, civil engineering, industrial robots, sports and leisure applications, etc., because of their high strength and elastic modulus. Further, PAN-based carbon fibers are mainly used in the field of utilizing their strength, and pitch-based carbon fibers are often used in the field of utilizing elastic modulus. In recent years, efficient use of energy represented by energy saving has been attracting attention, and on the other hand, heat generation due to high-speed CPU or Joule heat of electronic circuits is regarded as a major problem. Further, in the case of an electroluminescent element which is electronically injected as a principle of light emission, it is also a significant problem and is apparently present. On the other hand, in the process of forming various components, an environmentally-friendly process is required, and as a countermeasure, a so-called lead-free solder to which lead is not added is being replaced. Lead-free solders require a high efficiency of process heat because they have a higher melting point than conventional lead solders. Moreover, in order to solve the problem of heat contained in the product and process, it is necessary to achieve efficient processing (thermal management) of the heat -5 - 201118121. In general, carbon fiber can be said to have a high heat conductivity compared with other synthetic polymers, but for thermal management purposes, further improvement in thermal conductivity is examined. However, the thermal conductivity of commercially available PAN-based carbon fibers is usually smaller than 200 W/(m • K). This is because the PAN-based carbon fiber is a so-called non-graphitizable carbon fiber, and it is very difficult to increase the graphite system which is responsible for the thermal conductivity. On the other hand, the pitch-based carbon fiber is called an easily graphitizable carbon fiber, and since the graphite property can be improved as compared with the PAN-based carbon fiber, it is easy to achieve high thermal conductivity. Therefore, a highly thermally conductive material which is considered to be effective in exhibiting a thermal conductivity shape has a possibility of realization. Next, the characteristics of the shaped body used in thermal management are examined. Generally, carbon fibers exhibit electrical conductivity. Therefore, the composition in which the carbon fibers are combined with the matrix exhibits electrical conductivity. However, the aforementioned CPU or electronic circuit is often mounted on an insulated base or the like. Therefore, it is difficult to use a composition of carbon fibers for an electronic base system. Patent Documents 1 and 2 propose a method of coating an insulating layer on a thermally conductive composition. However, since it is not processed for the thermal conductive material, the insulation treatment corresponding to the complicated molded body is difficult. Further, Patent Document 3 proposes an insulating layer made of cerium oxide, and Patent Document 4 proposes a method of coating a thermally conductive chelating material with an insulating layer made of vermiculite or carbonized sand. However, the insulating layer made of the inorganic compound is brittle, and the coating is peeled off when it is kneaded with the resin, and the insulation is difficult to maintain. Among them, the tantalum carbide has a high hardness and causes damage to the kneading machine and the like. (Patent Document 1) JP-A-2008-208 3 1 6 Publication No. 201118121 (Patent Document 2) Japanese Patent Publication No. 2 0 0 8 - 2 0 5 4 5 (Patent Document 3) Special Opening 2 Ο Ο 7 - 1 2 Japanese Laid-Open Patent Publication No. Hei 2 0 0 7 - 1 0 7 1 5 1 SUMMARY OF THE INVENTION An object of the present invention is to provide an insulated pitch-based graphitized short fiber in a matrix The network has excellent formation ability and high thermal conductivity and insulation. Moreover, an object of the present invention is to provide a thermally conductive composition comprising at least one type of matrix component selected from the group consisting of an insulating pitched graphitized short fiber and a thermoplastic resin, a thermosetting resin, and a rubber. Shaped bodies formed by them. Means for Solving the Problems In order to obtain a review of the heat-conducting material that exhibits high thermal conductivity and exhibiting insulating properties, the present inventors have found that the pitch-based graphitized short fibers having excellent thermal conductivity are the core, and A melting point of 50 t or less and a precursor liquid or a precursor thereof or a resin which is soluble in at least one type of solvent is used to obtain a heat conductive material having high thermal conductivity and insulation. The invention is achieved. The present invention relates to an insulated pitch-based graphitized short fiber characterized by having a melting point of 250 ° C or lower and a precursor thereof being liquid, or a precursor or a solvent which is soluble in at least one kind of the precursor itself. Resin in the resin, coated surface. According to the present invention, an insulating pitch-based graphitized short fiber having both high thermal conductivity and insulating properties can be provided, whereby an insulating thermally conductive composition and a molded body thereof can be obtained. Thereby, it is possible to apply an electronic device, an electronic base, or the like that requires high heat dissipation characteristics. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in order. [Insulating pitch-based graphitized short fiber] The insulating pitch-based graphitized short fiber of the present invention is characterized by having a melting point of not more than 250 ° C on the surface, and the precursor is liquid or dissolved in a solvent The pitch of the resin layer is a graphitized short fiber. The insulative pitch-based graphitized short fiber has a resin layer formed by coating on the surface. For the purpose of insulating the graphitized short fibers, the surface of the graphitized short fibers is preferably almost completely covered by the resin layer. The pitch-based graphitized short fibers have a specific resistance of 1 〇 4 Ω · cm and exhibit conductivity. Further, even when it is mixed with a resin to form a molded article, the molded article exhibits electrical conductivity. Therefore, it is difficult to use a heat countermeasure such as a portion where the conductivity of the sealant is unfavorable. Relatively speaking, the general resin system has a grade of more than 1014 Ω·cm, and exhibits high insulation. Therefore, by coating each of the pitch-based graphitized short fibers with a resin, it is possible to insulate the pitch-based graphitized short fibers. However, the resin generally has a thermal conductivity that is significantly shorter than that of the asphalt-based graphitization. Therefore, when the pitch-based graphitized short fibers are insulated by a resin, it is necessary to coat with a small amount of resin. Therefore, the resin precursor or the solution in which the resin is dissolved is required to be in a liquid state. This is because if the coating agent is in a liquid form, the resin layer can be uniformly coated on the pitch-based graphitized short fibers to suppress the amount of the resin. The specific resistance of the insulated pitch-based graphitized short fibers of the present invention is preferably 1.0 x 10 〇 6 D.cm or more. If the specific resistance is less than l_0xl06Q.cm, the specific resistance of the molded article cannot be expected to give a high resistance. Further, the specific resistance of the insulative pitch-based graphitized short fibers is substantially 1.0x1 〇Ι 4 Ω. cm ° The insulating pitch-based graphitized short fibers of the present invention preferably have uniform insulation formed on the surface. The layer of pitch-based graphitized short fibers, that is, the observation surface of the scanning electron microscope is substantially flat. In the observation field of the image observed in the scanning electron microscope at 800 to 1000 times, the unevenness and defects in one of the pitch-based graphitized short fibers are 10 or less, or In the observation field of the image observed by 2000 times, each of the irregularities and defects is less than 15 places. The term "concavity and convexity" as used herein means that the surface of the insulative pitch-based graphitized short fiber, that is, the coated surface has severe irregularities, specifically having a height or depth of 3 μm or more, when observed by a scanning electron microscope. Bump. The term "defect" means that no resin is coated on a part of the insulating pitch-based graphitized short fibers, and a part of the surface of the pitch-based graphitized short fibers is exposed when observed by a scanning electron microscope. The insulating pitch-based graphitized short fiber of the present invention is preferably used in an amount of from 1 to 10 parts by weight based on 100 parts by weight of the pitch-based graphitized short fibers of -9 - 201118121. When the amount of the resin to be coated is 1 part by weight or less, the pitch-based graphitized short fibers cannot be sufficiently coated, and insulation properties cannot be expected. On the other hand, when the amount of the resin to be coated is 10 parts by weight or more, the resin for coating the pitch-based graphitized short fibers is too large, and when the molded article is formed, it is difficult to obtain high thermal conductivity. It is preferably 3 to 7 parts by weight, more preferably 3 to 5 parts by weight, per 100 parts by weight of the pitch-based graphitized short fibers. [Coated Resin] The properties required for the resin for coating the pitch-based graphitized short fibers include a melting point of not more than 25 ° C. When a thermoplastic resin is used as the matrix, the mixture is kneaded at a temperature equal to or higher than the melting point of the matrix. When the melting point of the applied resin does not reach the melting point of the matrix, it is difficult to maintain the insulating property because the applied resin is melted and removed. Therefore, it is required to have a melting point of not more than 250 ° C or more above the melting point of many thermoplastic resins. The so-called "melting point below 250 °C" means that the melting point exceeds 250 ° C or does not have the melting point itself. More preferably, it does not have a melting point of 300 ° C or less. The melting point can be measured by a differential scanning calorimeter or the like. Further, from the viewpoint of being able to coat the pitch-based graphitized short fibers and to be immobilized on the surface of the pitch-based graphitized short fibers, the resin used for coating requires the precursor to be liquid, or the precursor or itself. It is soluble in at least one type of solvent. The term "soluble in solvent" as used herein means, in particular, from 0 to 10 parts by weight of the precursor or tree-10-201118121 lipid at 20 ° C to below the solvent relative to 100 parts by weight of the solvent. Dissolved at a temperature of 1 〇t. The resin to be coated is not particularly limited as long as it does not have a melting point of 25 〇〇c and its precursor is a liquid 'or precursor or a substance which is soluble in at least one kind of solvent. Preferably, a thermosetting resin, an aromatic polyamine, or an aromatic polyimine 'aliphatic polyimine is mentioned. The thermosetting resin is not particularly limited, and specific examples thereof include an epoxy resin, a thermosetting acrylic resin, a urethane resin, and a polyoxymethylene resin. Among them, the epoxy resin is particularly excellent in affinity with the pitch-based graphitized short fibers. The pitch of the pitch-based graphitized short fibers and the resin is high, and even the pitch-based graphitized short fibers and the matrix insulated by the resin are mixed. When the molded article is produced, the insulating resin is also less likely to be peeled off from the pitch-based graphitized short fibers, and tends to maintain high insulation properties. The epoxy resin is not particularly limited, and may be a thermosetting reaction of a main component of a resin before curing and a curing agent. The main component is an aliphatic epoxy resin or an aromatic epoxy resin containing bisphenol or the like. Further, examples of the curing agent include an amine curing agent and an acid anhydride curing agent. Further, a hardening catalyst may be used as needed. As the curing catalyst, there is an imidazole-based curing catalyst. These main agents, hardeners, and hardening catalyst components can be suitably used as needed. The aromatic polyamine is not particularly limited, and specifically, an aromatic dicarboxylic acid component derived from terephthalic acid and/or isophthalic acid, and 1,4-phenylenediamine and 1, 3-phenylenediamine, 3,4,-aminodiphenyl ether, 4,4'-diaminodiphenyl ether and 1,3-bis(3-aminophenoxy)benzene 11 - 201118121 A group of wholly aromatic polyamines and aromatic polyamines and aromatic copolymers of aromatic diamines selected from the group. The aromatic polyimine is not particularly limited, and specific examples thereof include aromatic tetracarboxylic dianhydride formed from pyromellitic anhydride and the like, and 4,4-diaminodiphenyl ether. A polymer of an aromatic diamine. The aliphatic polyimine is not particularly limited, and specifically, it may be exemplified by saturated alicyclic tetracarboxylic dianhydride, and/or bicyclo(2,2,2 )-oct-7-ene-2,3,5. a group of 6-tetracarboxylic dianhydride and/or 5-(2,5-dioxo-tetradecyl)-3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride At least one selected aliphatic tetracarboxylic dianhydride, and 1,3·bis(3-aminomethyl)cyclohexane, 4,4′-diaminodicyclohexyl-methane, double (2) -Aminoethoxy)ethane A polymer of at least one aliphatic diamine selected from the group consisting of N,N-bis(3-aminopropyl)methylamine and ethylenediamine. The aromatic polyamine, the aromatic polyimine, and the aliphatic polyimine may be a copolymer insofar as the properties are not lost. [Method of Coating Resin] The method of coating the resin is not particularly limited, and specific examples thereof include (1) a method of preparing an insulating solution for coating, or (2) a gas treatment method without a solvent. The insulating solution of (1) is a liquid precursor, and the solvent is mixed as needed in the liquid precursor, or the precursor or the resin is dissolved in the solvent. As a specific preferred solvent for constituting the insulating solution, in the case of the epoxy resin, in the case of the epoxy resin, it is preferred to use acetone or toluene for the mixture of the main component and the hardener of the resin before curing. Methyl ethyl ketone isobutyl ketone. In the case of the polyoxyxene resin, in the same manner, in the mixed solution of the main component and the curing agent of the resin before curing, it is preferable to use toluene or hexane. In the case of an aromatic polyamine, n, n-methylpyrrolidone, dimethylacetamide, and dimethylamine are dissolved. In the case of the aromatic polyimine, a precursor N,N-methylpyrrolidone can be mentioned. In the case of an aliphatic polyimine, a hydrazine-soluble hydrazine-methylpyrrolidone can be mentioned. As a specific method of (1), in the case of a thermosetting resin, an aromatic sulfimine or an aliphatic polyimine, it is necessary to add a solvent to add a precursor to obtain an insulating solution, and the mixed pitch is short. The fiber is coated with a necessary insulation by a method such as spraying or filtration, and then heat-treated to harden the resin. In the case of aromatic polyfluorene, an insulating solution is obtained by dissolving it in a solvent, and the pitch-based graphitized short fiber is coated with an insulating solution by spraying or filtering, and then dried. The method of removing the solvent. Specific examples of the gas treatment method (2) include a method in which a gas of a raw material compound of a resin is polymerized on a pitched inkized short fiber. Further, in the gas treatment method, in order to carry out the reaction on the pitch-based graphitization, it is preferred to impart a treatment to the pitch-based graphitized short fibers. Since the amount of the coating resin is preferably 1 to 1 part by weight for 1 part by weight of the pitch-based graphitization as described above, in the case of (1), the agent may be a base. In the process of pre-extraction of the pre-existing group and in the middle of the graphite solution, it is preferred to select the amount of the insulating solution after coating, so as to ensure the desired resin. the amount. Here, in the method of (1), if the amount of the insulating solution used for coating is too large, the solution and the mash are aggregated due to the surface tension of the solution or the like, and uniform coating becomes difficult. As a result, defects often occur in the insulating layer, and it is difficult to uniformly coat the entire material to achieve insulation. Further, most organic compounds or inorganic compounds are inferior in thermal conductivity to pitch-based graphitized short fibers. Therefore, when the pitch-based graphitized short fiber is insulated by an organic compound or an inorganic compound, it is necessary to form the insulating surface in a small amount as much as possible in order to suppress the decrease in thermal conductivity. Therefore, when forming an insulating surface, it is necessary to apply a small amount of uniform coating. The preferred weight ratio of the insulating solution is from 1 to 10 parts by weight based on 100 parts by weight of the pitch-based graphitized short fibers. When a solvent is used, the solvent is from 1,000 to 20,000 parts by weight based on 1 part by weight of the resin or the precursor. By pulling apart the distance between the dips and reducing the amount of the insulating solution contacting the surface of the crucible, the drying time can be shortened and the aggregation can be suppressed, and the coating of the insulating layer can be achieved. Alternatively, when the insulating layer is applied, if the solution is not used as in the gas treatment method of (2), aggregation can be avoided. In view of productivity, a spray drying method which can be continuously treated is preferred. [Spray Drying Method] In the spray drying method, a slurry obtained by a solution for forming an insulating layer and a pitch of graphitized short fibers is sprayed through a rotating disk or a nozzle to release a mist spray. When the spray is hit by hot air, the solvent is almost instantaneously dried, and the surface of the pitch-based graphitized short fibers can be coated. Further, when the thermosetting resin is used in the insulating layer -14, the hot air can be cured by the hot air, and the insulating layer having high heat resistance can be applied. The solution used in the spray method 'as long as it is a dispersible pitch-based graphitized short fiber' can dissolve or disperse the insulating layer forming material, and can be sprayed into a mist. From the viewpoint of volatility, it is preferred to use a boiling point. For organic solvents below 1 2 0 «C. The preferred solvent for the solution constituting the spray method is the same as those listed in the column of the above-mentioned insulating solution. The preferred weight ratio of the spray solution is from 1 to 10 parts by weight of the pitch-based graphitized short fibers. The solvent is from 1 Å to 20,000 parts by weight based on 100 parts by weight of the resin or the precursor. [Pitch-based graphitized short fiber] The pitch-based graphitized short fiber of the present invention is preferably a bituminized graphitized short fiber of a specific shape from the viewpoint of moldability at the time of filling or thermal conductivity. . The pitch-type graphitized short fibers of the present invention preferably have an average fiber diameter (D1) of 2 to 20 μm as observed by an optical microscope. When D1 is less than 2 μm, the number of the short fibers increases as the resin is compounded, so that the viscosity of the resin/short fiber mixture becomes high, and molding becomes difficult. On the other hand, when D1 exceeds 20 μm, the number of short fibers is reduced when the resin is combined with the resin, so that the short fibers are hard to come into contact with each other, and it is difficult to exhibit an effective thermal conductivity as a composite material. A preferred range of D1 is 5 to 15 μm, more preferably 7 to 13 μm. -15- 201118121 The pitch-based graphitized short fiber of the present invention is based on the pitch-type graphitized short fiber observed by an optical microscope, and the percentage of the fiber diameter dispersion (S1) to the average fiber diameter (D1) (CV値) is Good for 3 to 15%. The smaller the index of the deviation of the CV lanthanide fiber diameter, the higher the process stability and the smaller the deviation of the product. When the CV 値 is less than 3%, since the fiber diameter is extremely tidy, the amount of short fibers entering the gap of the pitch-based graphitized short fibers is reduced, and it is difficult to densely fill the pitch-based graphitized short fibers. As a result, it will be difficult to obtain a high-performance composite. On the other hand, when CV 大于 is more than 15%, when it is compounded with a resin, the dispersibility is deteriorated, and it becomes difficult to obtain a composite material having uniform properties. The CV 値 is preferably 5 to 13%. The CV system can be realized by adjusting the viscosity of the molten mesophase pitch during spinning, specifically, when the spinning is performed by the melt flow method, the melt viscosity of the nozzle hole at the time of spinning is adjusted to 5.0 to 25.0. It is realized by Pa*S. The pitch-based graphitized short fibers generally have two types of honing fibers which are formed by an average fiber length of less than 1 mm and which are formed by an average fiber length of 1 mm or more and less than 10 mm. Since the appearance of the honing fibers is powdery and excellent in dispersibility, the appearance of the diced fibers is close to a fibrous shape, so that the fibers are easily brought into contact with each other. The pitch-based graphitized short fiber in the present invention corresponds to a honing fiber, and the average fiber length (L1) is preferably from 20 to 500 μm. Here, the average fiber length is the average number of fibers, and the length gauge can be used under an optical microscope, and the specified number of sheets can be measured in a plurality of fields of view, and the average number of fibers can be determined. When L 1 is less than 2 Ο μιη, the short fibers are difficult to contact each other, and it is difficult to expect an effective thermal conductivity. On the other hand, when it is more than 5 〇〇μηη, when it is mixed with a resin, the viscosity of the base μ -16-201118121/short fiber mixture becomes high, and the formability tends to be low. More preferably, it is a range of 2 0 to 3 00 μπι. The method for obtaining such a pitch-based graphitized short fiber is not particularly limited, and the rotation speed of the cutter, the number of rotations of the ball mill, and the jet mill can be adjusted by adjusting the conditions of the honing, that is, the pulverization by a cutter or the like. The air flow rate, the number of collisions of the crusher, and the residence time in the honing device control the average fiber length. Further, the pitch-based carbonaceous short fibers can be adjusted by removing the pitch-based carbonaceous short fibers having a short fiber length or a long fiber length by a classification operation such as screening. The pitch-based graphitized short fiber of the present invention is composed of graphite crystals, and the crystallite size from the growth direction of the hexagonal mesh surface is preferably 30 nm or more. The crystallite size corresponds to the degree of graphitization in the growth direction of the hexagonal mesh surface, and must be a certain size or more in order to exhibit thermal properties. The size of the crystal growth of the hexagonal mesh surface can be obtained by X-ray diffraction. Measuring method For the concentration method, the analytical method can be applied to the method of learning vibration. The crystallite size of the growth direction of the hexagonal mesh surface can be obtained by using the ray from the (1 1 0) plane to obtain the pitch-based graphitized short fiber of the present invention, preferably at the fiber end of the transmission electron microscope. In the middle, the end faces of the graphene sheets are closed. When the end faces of the graphene sheets are closed, it is less likely to cause the occurrence of excess functional groups or the localization of electrons due to the shape. Therefore, no active point is generated in the dendritic graphitized short fibers, and when the resin is coated, the curing failure can be suppressed due to a decrease in the catalytic activity point. Further, it is possible to reduce the adsorption of water or the like. For example, even in the kneading with a resin which is hydrolyzed with polyester, it is possible to bring about an remarkable improvement in wet heat durability. In the field of view of a transmission electron microscope that is magnified from 500,000 to 17,011,181 to 400,000 times, the end face of the graphene sheet is preferably closed at 80%. In this case, if it is 80% or less, it is not preferable to cause the occurrence of an excessive functional group or the localization of electrons due to the shape and to promote the reaction with other materials. The blocking ratio of the end face of the graphene sheet is preferably 90% or more, more preferably 95% or more. The graphene sheet end face structure is largely out of phase depending on whether pulverization is carried out before graphitization or after pulverization after graphitization. In other words, when the pulverization treatment is performed after the graphitization, the graphene sheets grown by the graphitization are cut and broken, and the end faces of the graphene sheets are easily opened. On the other hand, when the pulverization treatment is carried out before the graphitization, the end faces of the graphene sheets are bent into a U-shape during the growth of the graphite, and it is easy to form a structure in which the ends of the pitch-based graphitized short fibers are exposed in the curved portion. Therefore, in order to obtain a pitch-based graphitized short fiber having a graphene sheet end face blocking ratio of more than 80%, it is preferred to carry out a graphitization treatment after pulverization. The surface of the side surface of the pitch-based graphitized short fiber of the present invention which is observed by a scanning electron microscope is preferably substantially flat. Here, the term "substantially flat" means that the pitch-based graphitized short fibers do not have severe irregularities such as a fibril structure. When there is a defect such as severe unevenness on the surface of the pitch-based graphitized short fiber, when the matrix resin is kneaded, the viscosity increases due to an increase in the surface area, and the formability is deteriorated. Therefore, the defect such as surface unevenness is preferably as small as possible. More specifically, in the observation field of the image observed at 1,000 times in the scanning electron microscope, the defect such as the unevenness is 10 or less. In the observation field of the image observed by 2000 times, each of the bumps and defects is 15 or less below -18-201118121. As a method of obtaining such a pitch-based graphitized short fiber, it is preferred to carry out a graphitization treatment after honing. A preferred method for producing the pitch-based carbon short fibers used in the present invention will be described below. The raw material of the pitch-based carbonaceous short fiber used in the present invention may, for example, be a condensed polycyclic hydrocarbon compound such as naphthalene or phenanthrene, a petroleum-based pitch or a condensed heterocyclic compound such as coal-based pitch. Among them, a condensed polycyclic hydrocarbon compound such as naphthalene or phenanthrene is preferred, and a mesophase pitch is particularly preferred. The mesophase pitch of the mesophase pitch is preferably at least 90%, more preferably 95% or more, still more preferably 99% or more. Further, the mesophase ratio of the mesophase pitch can be confirmed by observing the molten asphalt in a polarizing microscope. Further, the softening point of the raw material pitch is preferably from 2 3 0 °C to 340 °C. The infusible treatment must be treated at a temperature lower than the softening point. Therefore, if the softening point is lower than 260 ° C, at least a non-melting treatment must be carried out at a low temperature which does not reach the softening point, and as a result, the infusible system takes a long time and is not preferable. On the other hand, if the softening point exceeds 340 ° C, it must exceed a high temperature of 34 CTC in spinning, and it is not preferable because of the occurrence of thermal decomposition of the pitch, generation of bubbles in the yarn, and the like. The softening point is particularly preferably in the range of 2 50 ° C or more and 3 20 ° C or less, more preferably 260 ° C or more and 310 ° C or less. Further, the softening point of the raw material asphalt can be obtained by the Mettler method. The raw material leaching may be used in combination of two or more kinds as appropriate. Preferably, the intermediate phase ratio of the raw material of the combined raw material is at least 90%, and the softening point is 260 ° C or more and 34 ° C or less. -19- 201118121 Mesophase pitch is spun by a melt method, and then becomes a pitch-based graphitized short fiber by infusibility, carbonization, pulverization, and graphitization. Depending on the situation, there is also an import grading step after comminution. The following steps illustrate the preferred aspects. In the spinning method, there is no particular limitation and it can be adapted to the melt spinning method. Specifically, a normal spinning extension method in which a mesophase pitch discharged from a nozzle is pulled by a winder, a melt flow method using hot air as an atomizing source, and a mesophase pitch by centrifugal force can be cited. Centrifugal spinning method, etc. Among them, the melt flow method is preferably used for the purpose of controlling the form of the pitch-based carbon fiber precursor and improving the productivity. Therefore, the melt flow method will be described below with respect to the method for producing the pitch-based graphitized short fibers of the present invention. The shape of the spinning nozzle forming the pitch-based carbon fiber precursor may be any pattern. Usually, a true round shape is used, and a nozzle having an irregular shape such as an ellipse is also used in a timely manner. The ratio of the length (LN) of the nozzle hole to the diameter (DN) (LN/DN) is preferably in the range of 2 to 20. If the LN/DN exceeds 20, a strong shear force is imparted to the mesophase pitch passing through the nozzle, and a radial structure is exhibited in the fiber cross section. The appearance of the radial structure is unfavorable because it causes cracks in the fiber cross section during the graphitization process, causing a decrease in mechanical properties. On the other hand, if the LN/DN is less than 2, the raw material pitch cannot be cut, and as a result, it becomes a pitch-based carbon fiber precursor having a low alignment of graphite. Therefore, even if it is graphitized, the degree of graphitization cannot be sufficiently increased, and it is difficult to improve the thermal conductivity. In order to achieve the coexistence of mechanical strength and thermal conductivity, it is necessary to impart moderate shear to the mesophase pitch. Therefore, the ratio (LN/DN) of the length (LN) of the nozzle hole to the diameter (DN) of the hole -20-201118121 is preferably in the range of 2 to 20, and more preferably in the range of 3 to 12. The temperature of the nozzle at the time of spinning, the mesophase pitch is related to the shear rate when passing through the nozzle, the amount of air blown by the nozzle, the temperature of the wind, and the like, and is not particularly limited as long as the spinning state can be maintained. The condition may be that the melt viscosity of the mesophase pitch in the nozzle hole is in the range of 1 to 1 〇〇Pa·S. When the melt viscosity of the mesophase pitch passing through the nozzle is less than 1 Pa_s, the melt viscosity is too low to maintain the shape of the wire. On the other hand, when the melt viscosity of the mesophase pitch exceeds loop a·S, it is not preferable to form a radial structure in the fiber cross section due to strong shearing force to the mesophase pitch. In order for the shear force imparted to the mesophase pitch to be in the proper range and to maintain the fiber shape', the melt viscosity of the mesophase pitch through the nozzle must be controlled. Therefore, the melt viscosity of the mesophase pitch is preferably in the range of 1 to 1 〇 〇 p a . s, particularly preferably in the range of 3 to 30 Pa.s, more preferably in the range of 5 to 25 Pa.s. The pitch-based graphitized short fiber used in the present invention preferably has an average fiber diameter (D1) of 2 to 20 μm or less, and the control of the average fiber diameter of the pitch-based graphitized short fiber can be changed by changing the nozzle diameter or changing from the nozzle. The amount of raw asphalt to be discharged 'or change the draft ratio to adjust. The change in the draft ratio can be achieved by blowing a gas having a linear velocity of 1 〇〇 2 〇〇〇 〇 m per minute heated to 100 to 400 t to the vicinity of the refining point. The gas to be sprayed is not particularly limited. It is preferably air in terms of cost efficiency and safety. The sprinkling carbon fiber precursor system is added to a belt such as a metal mesh. -21 - 201118121 is a pitch-based carbon fiber precursor mesh (web). At that time, the weight per unit area can be adjusted by the belt transport speed, and if necessary, the laminate can be laminated by a method such as cross-laying. The basis weight of the pitch-based carbon fiber precursor mesh is preferably 150 to 1 000 g/m 2 in consideration of productivity and process stability. The thus obtained pitch-based carbon fiber precursor mesh can be infusible by a well-known method. And become a bitumen-based infusible fiber mesh. The non-melting system can be carried out in an oxidizing atmosphere using air or a gas containing ozone, nitrogen dioxide, nitrogen, oxygen, iodine or bromine in the air, and in consideration of safety and convenience, it is preferably carried out in the air. Further, any of the batch processing and the continuous processing can be handled, but in consideration of productivity, continuous processing is preferred. The infusibilization treatment can be carried out by heat treatment at a temperature of 150 to 350 ° C for a certain period of time. A better temperature range is 160 to 340 °C. The temperature increase rate is preferably 1 to 10 ° C / min, and the above temperature increase rate can be achieved by sequentially passing through a plurality of reaction chambers set at an arbitrary temperature in a continuous process. Considering the productivity and process stability, the preferred range of heating rate is 3 to 9 ° C / min. The pitch-based infusible fiber web is carbonized at a temperature of 600 to 2000 ° C in a vacuum or in a non-oxidizing atmosphere using an inert gas such as nitrogen, argon or helium to form a pitch-based carbon fiber mesh. Considering the cost side, the carbonization treatment should be carried out under normal pressure and nitrogen environment. Further, any of batch processing and continuous processing can be handled, but if productivity is considered, continuous processing is preferred. Carbonized asphalt carbon fiber mesh cloth, in order to become the desired fiber

S -22- 201118121 維長度’係實施切斷.破碎.粉碎等的處理。又，視情況 而定’實施分級處理。處理方式係按照所欲的纖維長度來 選定，但於切斷中適宜使用橫切機式、1軸、2軸及多軸旋 轉式等的刀具，於破碎、粉碎中適宜使用利用衝撃作用的 鍵式、針式、球式、珠式及桿式、利用粒子彼此的衝撞之 高速旋轉式、利用壓縮.扯裂作用的輥式、錐式及螺旋式 等的破碎機•粉碎機等。爲了得到所欲的纖維長度，亦可 以多種複數機來構成切斷與破碎•粉碎。處理環境係可爲 濕式、乾式的任一者。於分級處理中適宜使用振動篩式、 離心分離式、慣性力式、過濾式等的分級裝置等。所欲的 纖維長度係不僅可藉由機種的選定，也可藉由控制轉子. 旋轉刀等的旋轉數、供給量、刀間的間隙、系內滯留時間 等而得。又，使用分級處理時，所欲的纖維長度也可藉由 調整篩網孔徑等而得。 倂用上述切斷、破碎·粉碎處理、視情況的分級處理 所作成的瀝青系碳質短纖維，係加熱到2000〜3500 °C而石 墨化，成爲最終的瀝青系石墨化短纖維。石墨化係藉由艾 奇遜（Acheson)爐、電爐等來實施，於真空中或在使用 氮、氬、氪等的惰性氣體之非氧化性環境下等實施。 本發明中的瀝青系石墨化短纖維，以更提高與絕緣用 樹脂的親和性、確保絕緣性爲目的，亦可進行表面處理。 表面處理的方法係沒有特別的限定，具體地可舉出電沈積 處理、鍍敷處理、臭氧處理、電漿處理、酸處理等。 -23- 201118121 [導熱性組成物] 本發明的絕緣化之瀝青系石墨化短纖維係可與基質複 合而成爲導熱性組成物。此時，相對於1 〇〇重量份的基質 而言，添加3〜300重量份的絕緣化之瀝青系碳質短纖維。 少於3重量份的添加量，係難以充分確保導熱性。另一方 面，多於300重量份的絕緣化之瀝青系碳質短纖維對於基 質的添加常常是困難。相對於1〇〇重量份的基質而言，較 佳爲20〜100重量份。 基質較佳爲由熱塑性樹脂、熱硬化性樹脂、芳香族聚 醯胺樹脂及橡膠所成之群選出的至少1種。爲了使複合成 形體展現所欲的物性，亦可適宜混合此等基質而使用。 基質中所用的樹脂係可與絕緣化之瀝青系石墨化短纖 維中所用的樹脂同種類或不同種類。同種類時，可期待與 樹脂的分散性、接著性良好。 作爲可用於基質的熱塑性樹脂，可舉出聚烯烴類及其 共聚物（聚乙烯、聚丙烯、聚甲基戊烯、聚氯乙烯、聚偏 二氯乙烯、聚醋酸乙烯酯、聚乙烯醇、乙烯-醋酸乙烯酯 共聚物、乙烯-丙烯共聚物等的乙烯·α-烯烴共聚物等）、 聚丙烯酸類及其共聚物（聚丙烯酸甲酯等的聚丙烯酸酯等 )、聚丙烯酸類及其共聚物、聚縮醛類及其共聚物、氟樹 脂類及其共聚物（聚偏二氟乙烯、聚四氟乙烯等）、聚酯 類及其共聚物（聚對苯二甲酸乙二酯、聚對苯二甲酸丁二 酯、聚2,6-萘二甲酸乙二酯、液晶性聚合物等）、聚苯乙 烯類及其共聚物（苯乙烯-丙烯腈共聚物、ABS樹脂等）、 -24- 201118121 聚丙烯腈類及其共聚物、聚苯醒（PPE)類及其共聚物（ 亦含改性PPE樹脂等）、脂肪族聚醯胺類及其共聚物、聚 碳酸醋類及其共聚物、聚苯硫類及其共聚物、聚楓類及其 共聚物、聚醚碾類及其共聚物、聚酸腈類及其共聚物、聚 醚酮類及其共聚物、聚___類及其共聚物 '聚酮類及其 共聚物、彈性體、液晶性聚合物等。可單獨使用此等的一 種，也可適宜組合二種以上而使用。更佳爲構成基質成分 之熱塑性樹脂係由聚碳酸酯類 '聚對苯二甲酸乙二酯類、 聚對苯二甲酸丁二酯類、聚2,6 -萘二甲酸乙二酯類、尼龍 類、聚丙烯類、聚乙烯類、聚醚酮類、聚苯硫類、及丙烯 腈-丁二烯-苯乙烯系共聚合樹脂類所成之群選出的至少一 種之樹脂。 又，作爲可用於基質的熱硬化性樹脂，可舉出環氧樹 脂、熱硬化性丙烯酸樹脂、胺基甲酸乙酯樹脂、聚矽氧樹 脂類、酚樹脂、熱硬化型改性PPE樹脂、及熱硬化型PPE 樹脂、聚醯亞胺樹脂及其共聚物、芳香族聚醯胺醯亞胺樹 脂及其共聚物等’可單獨使用此等的一種，也可適宜組合 二種以上而使用。 還有’作爲可用於基質的芳香族聚醯胺樹脂’可例示 由對苯二甲酸及/或間苯二甲酸所成的芳香族二羧酸成分 、與由1，4-苯二胺、1>3_苯二胺、3,4，_二胺基二苯基醚、 4,4’-二胺基二苯基醚及13 —雙（3_胺基苯氧基）苯所成之 群選出的至少一種之芳香族二胺成分而來的全芳香族聚醯 胺。 -25- 201118121 可用於基質的橡膠係沒有特別的限定，有天然 NR)、丙烯酸橡膠、丙烯腈丁二烯橡膠（NBR橡膠 戊二烯橡膠（IR)、胺基甲酸乙酯橡膠、乙烯丙烯 EPM)、環氧氯丙烷橡膠、氯丁二烯橡膠（CR)、 橡膠及其共聚物、苯乙烯丁二烯橡膠（SBR) 、丁 膠（BR) 、丁基橡膠等。 本發明的組成物係混合絕緣化之瀝青系石墨化 與基質而製作，於混合之際，適宜使用捏合機、各 機、摻合機、輥、擠壓機、硏磨機、自公轉式的攪 之混合裝置或混煉裝置。此處，當基質樹脂爲熱硬 脂或橡膠時，於混合硬化前的樹脂或橡膠與絕緣化 系石墨化短纖維後，可使進行成形及硬化反應。 爲了更提高本發明的導熱性組成物之導熱率， 亦可添加碳化矽被覆瀝青系石墨化短纖維以外的塡 體地，可舉出氧化鋁、氧化鎂、氧化矽、氧化鋅等 氧化物、氫氧化鋁、氫氧化鎂等的金屬氫氧化物、 、氮化鋁等的金屬氮化物、氧化氮化鋁等的金屬氧 、碳化矽素等的金屬碳化物、鑽石等的碳材料等。 於機能而適宜添加此等。又，亦可倂用2種類以上 上述化合物多爲密度比瀝青系石墨化短纖維大者， 化爲目的時，必須留意添加量或添加比率。又，添 性塡料時，由於無法達成絕緣性的維持，故必須留: 再者，爲了更提高成形性、機械物性等的其它 亦可按照所需要的機能，適宜添加玻璃纖維、鈦酸 橡膠（ )、異 橡膠（ 聚矽氧 二烯橡 短纖維 種混合 拌機等 化性樹 之瀝青 視需要 料。具 的金屬 氮化硼 氮化物 可對應 。惟， 以輕量 加導電 K ° 特性， 狎鬚晶 -26· 201118121 、氧化鋅鬚晶、棚化鋁鬚晶、氮化硼鬚晶、芳族聚醯胺纖 維、氧化鋁纖維、碳化矽素纖維、石綿纖維、石膏纖維等 的纖維狀塡料。亦可併用2種類以上的此等。亦可按照需 要而適宜添加石灰石、沸石、絹雲母、高嶺土、雲母、黏 土、葉蠟石、膨土、石綿、滑石、砂酸銘等的砂酸鹽、碳 酸鈣、碳酸鎂、白雲石等的碳酸鹽、硫酸鈣、硫酸鋇等的 硫酸鹽、玻璃珠、玻璃小片及陶瓷珠等的非纖維狀塡料。 此等亦可爲中空，再者亦可倂用2種類以上的此等。惟， 上述化合物多爲密度比瀝青系石墨化短纖維者，以輕量化 爲目的時，必須留意添加量或添加比率。 又’視需要亦可將複數的其它添加劑加到組成物中。 作爲其它添加劑，可舉出脫模劑、難燃劑、乳化劑、軟化 劑 '可塑劑、界面活性劑。 更具體地，說明組成物的用途。該組成物係可用作爲 在電子機器等中用於將半導體元件或電源 '光源等的電子 零件所產生的熱有效果地往外部散發之散熱構件、傳熱構 件或彼等的構成材料等。 當基質係由熱塑性樹脂所成的導熱性組成物時，可藉 由從射出成形法、加壓成形法、壓延成形法、輥成形法、 擠壓成形法、澆鑄成形法及吹塑成形法所成之群選出的至 少一種之方法來成形，而得到成形體。而且，薄片狀成形 體係可藉由輥的壓出、模口的壓出等的擠壓成形法而進行 成形。成形條件係依賴於成形手法與基質，可在比該樹脂 之熔融黏度高的溫度之狀態下實施成形。 -27- 201118121 當基質係由熱硬化性樹脂所成的導熱性組成物時，可 使用硬化前的樹脂來施行成形，可藉由從射出成形法、加 壓成形法、壓延成形法、輥成形法、擠壓成形法及澆鑄成 形法所成之群選出的至少一種之方法來成形，而得到成形 體。成形條件係依賴於成形手法與基質，可舉出於成形中 或適切的模具中，賦予該樹脂的硬化溫度等之方法。 當基質係由芳香族聚醯胺樹脂所成的導熱性組成物時 ，可使芳香族聚醯胺樹脂溶解於溶劑中，於其中混合瀝青 系石墨化短纖維，使用鑄造法來成形。此處，作爲溶劑， 只要芳香族聚醯胺樹脂能溶解，則沒有特別的限定，具體 地可使用Ν，Ν·二甲基乙醯胺、N-甲基吡咯烷酮等的醯胺系 溶劑。 當基質係由橡膠所成的導熱性組成物時，可藉由從加 壓成形法、壓延成形法、輥成形法所成之群選出的至少一 種之方法來成形，而得到成形體。成形條件係依賴於成形 手法與基質，可舉出賦予該橡膠的加硫溫度等之方法。 可由該導熱性組成物得到複合物、薄片、油脂、接著 劑等的成形材料或導熱性成形體。本發明包含如此地由上 述導熱性組成物所得之成形體。 實施例 以下顯示實施例，惟本發明不受此等所限制。 再者，本實施例中的各値係依照以下的方法來求得。 (1 )絕緣化之瀝青系石墨化短纖維及瀝青系石墨化 -28- 201118121 短纖維的平均纖維直徑係依據〗IS R7607，於光學顯微鏡 下使用刻度尺來測定60條，由其平均値求得。 (2 )絕緣化之瀝青系石墨化短纖維及瀝青系石墨化 短纖維的個數平均纖維長係使用SEI SHIN企業製PIT A1來測 定1 5 00條，由平均値求得。 (3 )瀝青系石墨化短纖維的雛晶尺寸係測定來X射 線繞射中所出現的（1 1 〇 )面之反射，藉由學振法求得。 (4)瀝青系石墨化短纖維的端面係用透射型電子顯 微鏡以100萬倍的倍率進行觀察，於照片上放大400萬倍， 確認石墨烯薄片。於瀝青系石墨化短纖維藉由透射型電子 顯微鏡的纖維末端觀察中，觀察5條之纖維末端的50〜250 萬倍之石墨烯薄片端面影像，計測纖維末端的石墨烯薄片 端面之全長A (nm)與端面彎曲成U字狀的部分之長度B( nm )，藉由閉鎖率（％) =Β/Αχ100來求得閉鎖率。 (5 )絕緣化之瀝青系石墨化短纖維及瀝青系石墨化 短纖維的表面係用掃描型電子顯微鏡以2000倍的倍率進行 觀察，確認缺陷及凹凸。 (6 )絕緣化之瀝青系石墨化短纖維的熱硬化樹脂硬 化物之塗覆量，係在大氣環境下於5〇〇 °C將絕緣化之瀝青 系石墨化短纖維保持3小時，由加熱前後的重量差來算出 〇 (7 )絕緣化之瀝青系石墨化短纖維的比電阻係使用 三菱化學分析科技製MCP-PD51來求得。 (8 )導熱性組成物的比電阻係使用三菱化學分析科 -29- 201118121 技製Hiresta UP來求得。 (9)導熱性組成物的導熱率係使用京都電子工業製 QTM-500來求得。 參考例1 以由縮合多環烴化合物所成的瀝青當作主原料。光學 異向性比例爲100%，軟化點爲2 8 3 °c。使用直徑0.2mmφ的 孔之帽，由狹縫以每分鐘5 500m的線速度噴出加熱空氣， 牽引熔融瀝青而製作平均直徑1 1.2 μηι的瀝青系短纖維。此 時的紡絲溫度爲325°C，熔融黏度爲17.5Pa*S ( 175泊）。 在帶上補集所紡出的纖維而成爲蓆（mat)，再藉由交叉 鋪網而成爲由單位面積重量35 Og/m2的瀝青系碳纖維前驅 物所成之瀝青系碳纖維前驅物網布。 將此瀝青系碳纖維前驅物網布在空氣中由17〇°C以5°C/ 分鐘的平均升溫速度升溫到3 00°C爲止而不熔化，再於 800°C進行煅燒。使用刀具（TURBO工業製）以900rpm將 此瀝青系碳纖維網布粉碎，在3000°C石墨化》 瀝青系石墨化短纖維的平均纖維直徑爲8 · 1 μπι，纖維 直徑分散對平均纖維直徑之比（CV値）爲1 1 %。個數平均 纖維長爲ΙΟΟμπι，來自六角網面的成長方向之結晶尺寸爲 8Onm。 瀝青系石墨化短纖維的端面係藉由透射型顯微鏡的觀 察，確認石墨烯薄片已關閉。石墨烯薄片的閉鎖率爲 90.3%。又，表面係藉由掃描型電子顯微鏡的觀察’凹凸 -30- 201118121 爲1個而實質上平滑。 瀝青系石墨化短纖維的比電阻爲2.5χ1 〇·4Ω. cm。 實施例1 使用自公轉混合機（THINKY公司製註冊商標「脫泡 練太郎ARV3 10」）將100重量份的環氧樹脂主劑（日本環 氧樹脂製註冊商標「Epicoat 871」）、30重量份的環氧樹 脂硬化劑（日本環氧樹脂製註冊商標「Epicure FL240」） 與2 0重量份的參考例1所作成之瀝青系石墨化短纖維混合3 分鐘後’進行過濾以去除多餘的硬化前之樹脂。將此在 1 5 〇 °C處理2小時而得到絕緣化之瀝青系石墨化短纖維。圖 1中顯示所得的絕緣化之瀝青系石墨化短纖維的掃描型電 子顯微鏡觀察照片’可確認環氧樹脂塗佈在石墨化短纖維 的表面上。凹凸及缺陷係沒有觀察到。 相對於100重量份的瀝青系石墨化短纖維而言，環氧 樹脂的塗覆量爲7.8重量份。絕緣化之瀝青系石墨化短纖 維的比電阻爲5.0xl08Q.cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 9.8μηι ’纖維直徑分散對平均纖維直徑之比（CV値）爲 12%。個數平均纖維長爲100μιη。 實施例2 使90重量份的環氧樹脂主劑（日本環氧樹脂製註冊商 標「Epicoat 806」）、11〇重量份的環氧樹脂硬化劑（曰 -31 - 201118121 本環氧樹脂製註冊商標「Epicure YH3 07」）份、2重量份 的環氧樹脂硬化觸媒（日本環氧樹脂製商品名「IMB II 02 」）溶解於200重量份的乙基甲基酮中，使用自公轉混合 機（THINKY公司製註冊商標「脫泡練太郎ARV310」）與 30重量份的參考例1所作成之瀝青系石墨化短纖維混合3分 鐘後，進行過濾以去除多餘的硬化前之樹脂。將此在 1 50 t處理2小時而得到絕緣化之瀝青系石墨化短纖維。表 面觀察的結果可確認環氧樹脂對瀝青系石墨化短纖維的塗 佈。凹凸及缺陷係沒有觀察到。相對於1 00重量份的瀝青 系石墨化短纖維而言，環氧樹脂的塗覆量爲3.1重量份。 絕緣化之瀝青系石墨化短纖維的比電阻爲7.〇χ1 05Ω· cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 9.0μηι，纖維直徑分散對平均纖維直徑之比（CV値）爲 11%。個數平均纖維長爲1〇〇μιη。 實施例3 使90重量份的環氧樹脂主劑（日本環氧樹脂製註冊商 標「Epicoat 806」）、110重量份的環氧樹脂硬化劑（曰 本環氧樹脂製註冊商標「Epicure YH307」）、2重量份的 環氧樹脂硬化觸媒（日本環氧樹脂製註冊商標「IMB II 02 」）溶解於1〇〇重量份的乙基甲基酮中，使用自公轉混合 機（THINKY公司製註冊商標「脫泡練太郎ARV310」）與 3 0重量份的參考例1所作成之瀝青系石墨化短纖維混合3分 鐘後，進行過濾以去除多餘的硬化前之樹脂。將此在 -32- 201118121 表塗 。 的 維維 纖纖 短短 化化 墨墨 石石 系系 青青 瀝瀝 之對 化脂 緣樹 絕氧 到環 得認 而確 時可 小果 2 結 mi 1 理 cm察 0°觀 15面 爲 阻 電 比 β 句0 0^ 察氧ί 觀環短 有，七、沒一一_ ΐ 係而石 陷維系 缺纖青 及短瀝 凸化之 凹墨化 。 石緣 佈系絕 旨 青 。 瀝份的量， 份重 Ω 量8 7 4 &lj 01爲 10量 於覆 對塗 相的 ο m 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 9.3μιη’纖維直徑分散對平均纖維直徑之比（CV値）爲 11%。個數平均纖維長爲ΙΟΟμηι。 實施例4 使用自公轉混合機（THINKΥ公司製註冊商標「脫泡 練太郎ARV310」），將90重量份的環氧樹脂主劑（日本 環氧樹脂製註冊商標「Epicoat 8 06」）、110重量份的環 氧樹脂硬化劑（日本環氧樹脂製註冊商標「Epicure YH3〇7」）、2重量份的環氧樹脂硬化觸媒（日本環氧樹 脂製註冊商標「IMBI102」）與25重量份的參考例1所作成 之瀝青系石墨化短纖維混合3分鐘後，進行過濾以去除多 餘的硬化前之樹脂。將此在1 5 0 °C處理2小時而得到絕緣化 之瀝青系石墨化短纖維。圖2中顯示所得的絕緣化之瀝青 系石墨化短纖維的掃描型電子顯微鏡觀察照片，可確認環 氧樹脂塗佈在石墨化短纖維的表面上，但在塗佈面上觀察 到凹凸爲4個。缺陷係沒有觀察到。 相對於1〇〇重量份的瀝青系石墨化短纖維而言，環氧 樹脂的塗覆量爲9.2重量份。絕緣化之瀝青系石墨化短纖 -33- 201118121 維的比電阻爲3.〇xl01()n_cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 10.3μπι，纖維直徑分散對平均纖維直徑之比（CV値）爲 1 1 %。個數平均纖維長爲1 〇 〇 μ m。 實施例5 使5重量份的二液硬化型聚矽氧樹脂（東麗DOW聚矽 氧製商品名「SE 1 740A&B」）溶解於200重量份的甲苯中 ，使用自公轉混合機（THINKY公司製註冊商標「脫泡練 太郎ARV310」）與100重量份的參考例1所作成之瀝青系 石墨化短纖維混合3分鐘後，使甲苯揮發。將此在150°C處 理2小時而得到絕緣化之瀝青系石墨化短纖維。表面觀察 的結果可確認聚矽氧樹脂對瀝青系石墨化短纖維的塗佈》 凹凸及缺陷係沒有觀察到。 相對於1〇〇重量份的瀝青系石墨化短纖維而言，聚矽 氧樹脂的塗覆量爲4.8重量份。絕緣化之瀝青系石墨化短 纖維的比電阻爲7.0χ107Ω·£：πι。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 9·0μιη，纖維直徑分散對平均纖維直徑之比（CV値）爲 11%。個數平均纖維長爲ΙΟΟμηι。 實施例6 使2重量份的芳香族聚醯胺樹脂（帝人科技產品製註 冊商標「Technora」）溶解於200重量份的Ν-甲基吡咯烷 «% -34- 201118121 酮中，使用自公轉混合機（ΤΗ INKY公司製註冊商標「脫 泡練太郎ARV3 10」）與100重量份的參考例】所作成之瀝 青系石墨化短纖維混合3分鐘而得到混合漿體。將此在 2 〇〇 °C於旋轉式蒸發器內進行乾燥。於同濃度的芳香族聚 醯胺樹脂溶液中重複浸漬、乾燥所得之表面處理瀝青系石 墨化短纖維3次，而得到絕緣化之瀝青系石墨化短纖維。 表面觀察的結果確認芳香族聚醯胺樹脂對瀝青系石墨化短 纖維的塗佈。凹凸及缺陷係沒有觀察到。 相對於100重量份的瀝青系石墨化短纖維而言，芳香 族聚醯胺樹脂的塗覆量爲5.9重量份。絕緣化之瀝青系石 墨化短纖維的比電阻爲2.1x1 06Ω· cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 9·0μηι，纖維直徑分散對平均纖維直徑之比（CV値）爲 11%。個數平均纖維長爲ΙΟΟμπι。 實施例7 使用自公轉混合機（THINKΥ公司製註冊商標「脫泡 練太郎ARV3 10」），將由100重量份的環氧樹脂主劑（曰 本環氧樹脂製註冊商標「Epicoat 871」）、30重量份的環 氧樹脂硬化劑（日本環氧樹脂製註冊商標「Epicure FL240 」）份所成的混合液1 00重量份與1 〇〇重量份的實施例1所 作成的絕緣化之瀝青系石墨化短纖維混合6分鐘而成爲混 合漿體。用真空加壓機（北川精機製）將此漿體加壓加工 而得到厚度〇.5mm的平板狀之複合組成物，在l5〇°C硬化4 -35- 201118121 小時而作成導熱性組成物。導熱性組成物的比電阻爲 8.5χ109Ω·(^ηιβ導熱性組成物的導熱率爲6.2W/(m，K)。 實施例8 使用自公轉混合機（THINKY公司製註冊商標「脫泡 練太郎ARV310」），將由90重量份的環氧樹脂主劑（曰 本環氧樹脂製註冊商標「Epicoat 806」）、110重量份的 環氧樹脂硬化劑（日本環氧樹脂製註冊商標「Epicure 3 07 」）、2重量份的環氧樹脂硬化觸媒（日本環氧樹脂製商 品名「IMBI1 02」）所成的混合液100重量份與100重量份 的實施例2所作成的絕緣化之瀝青系石墨化短纖維混合6分 鐘而成爲混合漿體。用真空加壓機（北川精機製）將此漿 體加壓加工而得到厚度〇.5mm的平板狀之複合組成物，在 1 50°C硬化4小時而作成導熱性組成物。導熱性組成物的比 電阻爲6.5Χ107Ω·(：ηι»導熱性組成物的導熱率爲8.3W/(m· K)。 實施例9 除了所用的絕緣化之瀝青系石墨化短纖維爲實施例3 所作成者以外，與實施例7同樣地作成導熱性組成物。導 熱性組成物的比電阻爲3.5 xl 08Ω· cm。導熱性組成物的導 熱率爲 7.3W/ ( m.K )。 實施例1 〇 μ -36- 201118121 除了所用的絕緣化之瀝青系石墨化短纖維爲實施例4 所作成者以外，與實施例7同樣地作成導熱性組成物。導 熱性組成物的比電阻爲7.2 X 1 0 1 1 Ω · c m。導熱性組成物的導 熱率爲 4.8W/ ( m . K )。 實施例1 1 除了所用的絕緣化之瀝青系石墨化短纖維爲實施例5 所作成者以外，與實施例7同樣地作成導熱性組成物。導 熱性組成物的比電阻爲7 · 5 X 1 08Ω ♦ cm。導熱性組成物的導 熱率爲 7. 1 W/ ( m . K )。 實施例1 2 除了所用的絕緣化之瀝青系石墨化短纖維爲實施例6 所作成者以外，與實施例7同樣地作成導熱性組成物。導 熱性組成物的比電阻爲1 ·0χ 1 07Ω · cm。導熱性組成物的導 熱率爲 5.9W/ ( m · K )。 實施例1 3 使用自公轉混合機（THINKY製脫泡練太郎ARV-310 )’將1 0 0重量份的參考例1所作成之瀝青系石墨化短纖維 、5重量份的聚矽氧樹脂（東麗.道康寧製，SE1740)、 3 00重量份的甲苯（和光純藥製）混合3分鐘，而成爲複合 漿體。用噴霧乾燥機（柴田科學製，B - 2 9 0 )對此實施噴霧 乾燥處理’而得到絕緣化之瀝青系石墨化短纖維。處理溫 -37- 201118121 度爲200°C。 相對於100重量份的瀝青系石墨化短纖維而言，絕緣 層塗覆量爲5重量份。絕緣化之瀝青系石墨化短纖維的比 電阻爲 5.0xl〇12n.cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 8.5μηι，纖維直徑分散對平均纖維直徑之比（CV値）爲 12%。個數平均纖維長爲ΙΟΟμιη。表面觀察的結果可確認 聚矽氧樹脂對瀝青系石墨化短纖維的塗覆。凹凸及缺陷係 沒有觀察到。 實施例1 4 使用自公轉混合機（ΤΗΙΝΚΥ製脫泡練太郎ARV-310 )，將1 〇〇重量份的參考例1所作成的瀝青系石墨化短纖維 、2.25重量份的環氧樹脂主劑（日本環氧樹脂製註冊商標 「Epicoat 8 06」）、2.75重量份環的氧樹脂硬化劑（日本 環氧樹脂製註冊商標「Epicure 307」）、0.05重量份的環 氧樹脂硬化觸媒（日本環氧樹脂製商品名「IMBI102」） 、3 00重量份的乙基甲基酮（和光純藥製）混合3分鐘，而 成爲複合漿體。用噴霧乾燥機（柴田科學製，B-290 )對此 實施噴霧乾燥處理，而得到絕緣化之瀝青系石墨化短纖維 。處理溫度爲200°C。 相對於1〇〇重量份的瀝青系石墨化短纖維而言，絕緣 層塗覆量爲5重量份。絕緣化之瀝青系石墨化短纖維的比 電阻爲 2.0xl012Q.cm。 £ -38- 201118121 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 8·5μπι ’纖維直徑分散對平均纖維直徑之比（CV値）爲 13% °個數平均纖維長爲1〇〇 μηι。表面觀察的結果可確認 環氧樹脂對瀝青系石墨化短纖維的塗佈，凹凸爲1個，缺 陷爲〇個。 實施例1 5 使用自公轉混合機（ΤΗΙΝΚΥ製脫泡練太郎ARV-3 10 )，將1 00重量份的參考例1所作成之瀝青系石墨化短纖維 、1.12重量份的環氧樹脂主劑（日本環氧樹脂製註冊商標 「Epicoat 806」）、1 . 3 8重量份的環氧樹脂硬化劑（日本 環氧樹脂製註冊商標「Epicure 307」）、0.02重量份的環 氧樹脂硬化觸媒（日本環氧樹脂製商品名「IMB 1102」） 、3 00重量份的乙基甲基酮（和光純藥製）混合3分鐘，而 成爲複合漿體。用噴霧乾燥機（柴田科學製，B-2 90)對此 實施噴霧乾燥處理，而得到絕緣化之瀝青系石墨化短纖維 。處理溫度爲200°C。 相對於1 〇〇重量份的瀝青系石墨化短纖維而言，絕緣 層塗覆量爲2.5重量份。絕緣化之瀝青系石墨化短纖維的 比電阻爲 8.9χ10ηΩ·(：πι。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 8.2μιη，纖維直徑分散對平均纖維直徑之比（CV値）爲 12%。個數平均纖維長爲100 μτη。表面觀察的結果可確認 環氧樹脂對瀝青系石墨化短纖維的塗佈，缺陷爲0個，凹 -39- 201118121 凸爲1個。 實施例1 6 使用自公轉混合機（THINKY製脫泡練太郎ARV-310 )，將100重量份的參考例1所作成之瀝青系石墨化短纖維 、5重量份的四乙氧基矽烷（和光純藥）、1重量份的28% 氨水（和光純藥製）、3 00重量份的乙醇（和光純藥製） 、75重量份的水混合3分鐘，而成爲複合漿體。用噴霧乾 燥機（柴田科學製，B-2 90)對此實施噴霧乾燥處理，而得 到絕緣化之瀝青系石墨化短纖維。處理溫度爲130°C。 相對於100重量份的瀝青系石墨化短纖維而言，絕緣 層塗覆量爲5重量份。絕緣化之瀝青系石墨化短纖維的比 電阻爲 S.OxloHn.cm。 絕緣化之瀝青系石墨化短纖維的平均纖維直徑爲 8.6μπι，纖維直徑分散對平均纖維直徑之比（CV値）爲 1 2%。個數平均纖維長爲1 〇〇μηι。表面觀察的結果可確認 聚矽氧凝膠皮膜對瀝青系石墨化短纖維的塗佈，缺陷爲0 個，凹凸爲3個。 實施例1 7 使用自公轉混合機（THINKY製脫泡練太郎ARV-3 10 )，將4 5重量份的實施例1 3所得的絕緣化之瀝青系石墨化 短纖維與100重量份的聚矽氧樹脂（東麗•道康寧製， SE1 740 )混合3分鐘，而成爲複合漿體。用真空加壓機（ -40- 201118121 北川精機製）將此漿體加壓加工而得到厚度〇.5mm的 狀之複合成形體，於1 3 (TC硬化2小時而作成導熱性組 。導熱性組成物的比電阻爲3 . 5 X 1 〇 13 Ω · c m。導熱性組 的導熱率爲4.9W/(m.K)。 實施例1 8 使用自公轉混合機（TH INKY公司製註冊商標「 練太郎ARV-310」），將45重量份的實施例14所得的 化之瀝青系石墨化短纖維與1〇〇重量份的聚矽氧樹脂 麗·道康寧製，SE1 74 0)混合3分鐘，而成爲複合漿體 真空加壓機（北川精機製）將此漿體加壓加工而得到 0.5mm的平板狀之複合成形體，於130°C硬化2小時而 導熱性組成物。導熱性組成物的比電阻爲LOxl 0Ι3Ω · 導熱性組成物的導熱率爲4.7W/(m_K)。 實施例1 9 使用自公轉混合機（THINKY公司製註冊商標「 練太郎ARV-3 10」），將45重量份的實施例15所得的 化之瀝青系石墨化短纖維與1〇〇重量份的聚矽氧樹脂 麗·道康寧製，SE1740)混合3分鐘，而成爲複合漿體 真空加壓機（北川精機製）將此漿體加壓加工而得到 0.5mm的平板狀之複合成形體，於130°C硬化2小時而 導熱性組成物。導熱性組成物的比電阻爲1.0x1 〇13Ω· 導熱性組成物的導熱率爲4.8W/ ( ιη·Κ)。 平板 成物 成物 脫泡 絕緣 (東 。用 厚度 作成 c m ° 脫泡 絕緣 (東 。用 厚度 作成 -41 · 201118121 實施例20 使用自公轉混合機（THINKY製脫泡練太郎ARV-310 )’將4 5重量份的實施例1 6所得的絕緣化之瀝青系石墨化 短纖維與100重量份的聚矽氧樹脂（東麗.道康寧製， SE1740)混合3分鐘，而成爲複合漿體。用真空加壓機（ 北川精機製）將此漿體加壓加工而得到厚度0.5mm的平板 狀之複合成形體，於1 30°C硬化2小時而作成導熱性組成物 。導熱性組成物的比電阻爲1 _ 0 X 1 0 13 Ω · cm。導熱性組成物 的導熱率爲5.1W/(m.K)。 比較例1 除了所用的絕緣化之瀝青系石墨化短纖維爲參考例1 所作成者以外’與實施例6同樣地作成導熱性組成物。導 熱性組成物的比電阻爲6.0 X 1 0·1 Ω . cm。導熱性組成物的導 熱率爲 9.3W/ ( m · K )。 產業上的利用可能性 本發明的絕緣化之瀝青系石墨化短纖維，係藉由不具 有2 5 0 °C以下的熔點’且其前驅物爲液狀可溶於溶劑中樹 脂，塗覆導熱率優異的瀝青系石墨化短纖維，而可一邊顯 示高的導熱性’一邊賦予絕緣性。藉此，可廣泛地使用於 要求高的散熱特性之電子機器、電子零件的散熱構件，使 熱管理成爲確實者。 •42- 201118121 【圖式簡單說明】 圖1係實施例1所得的絕緣化之瀝青系石墨化短纖維之 掃描型電子顯微鏡觀察照片。 圖2係實施例4所得的絕緣化之瀝青系石墨化短纖維之 掃描型電子顯微鏡觀察照片。S -22- 201118121 Dimension length is a process of cutting, crushing, crushing, etc. Also, depending on the situation, the classification process is implemented. The treatment method is selected according to the desired fiber length. However, a cutter such as a cross-cut type, a 1-axis, a 2-axis, and a multi-axis rotary type is preferably used for cutting, and a key using a punching action is suitably used for crushing and pulverizing. Type, needle type, ball type, bead type and rod type, high-speed rotary type that uses collision of particles, crusher, crusher, etc. which use compression, tearing, roll, cone and spiral. In order to obtain the desired fiber length, it is also possible to form cut, crush, and pulverize by a plurality of plural machines. The treatment environment can be either wet or dry. A classification device such as a vibrating screen type, a centrifugal separation type, an inertial force type, or a filtration type is preferably used in the classification process. The desired fiber length can be obtained not only by the selection of the model but also by controlling the number of rotations of the rotor, the rotary blade, the amount of supply, the gap between the knives, and the residence time in the system. Further, when the classification treatment is used, the desired fiber length can also be obtained by adjusting the sieve aperture or the like. The pitch-based carbon short fibers produced by the above-mentioned cutting, crushing, pulverizing treatment, and, if appropriate, classification treatment, are heated to 2000 to 3500 ° C to be graphiteized to form the final pitch-based graphitized short fibers. The graphitization is carried out by 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. The pitch-based graphitized short fiber of the present invention may be subjected to surface treatment for the purpose of further improving affinity with the insulating resin and ensuring insulation. The method of the surface treatment is not particularly limited, and specific examples thereof include electrodeposition treatment, plating treatment, ozone treatment, plasma treatment, acid treatment, and the like. -23-201118121 [Thermal composition] The insulative pitch-based graphitized short fiber of the present invention can be combined with a matrix to form a thermally conductive composition. At this time, 3 to 300 parts by weight of the insulating pitch-based carbonaceous short fibers are added to 1 part by weight of the substrate. When the amount is less than 3 parts by weight, it is difficult to sufficiently ensure thermal conductivity. On the other hand, it is often difficult to add more than 300 parts by weight of the insulative pitch-based carbonaceous staple fibers to the matrix. It is preferably 20 to 100 parts by weight based on 1 part by weight of the substrate. The substrate is preferably at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, an aromatic polyamide resin, and a rubber. In order to allow the composite molded body to exhibit desired physical properties, it is also possible to use these substrates as appropriate. The resin used in the matrix may be of the same kind or different kind as the resin used in the insulative pitch-based graphitized short fiber. When it is the same kind, it is expected that the dispersibility and adhesion to the resin are good. Examples of the thermoplastic resin usable in the matrix include polyolefins and copolymers thereof (polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, Ethylene/vinyl acetate copolymer, ethylene/α-olefin copolymer such as ethylene-propylene copolymer, etc., polyacrylic acid and copolymer thereof (polyacrylate such as polymethyl acrylate), polyacrylic acid and the like Copolymers, polyacetals and copolymers thereof, fluororesins and copolymers thereof (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyesters and copolymers thereof (polyethylene terephthalate, Polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, liquid crystal polymer, etc.), polystyrenes and copolymers thereof (styrene-acrylonitrile copolymer, ABS resin, etc.), -24- 201118121 Polyacrylonitriles and their copolymers, polystyrene (PPE) and their copolymers (including modified PPE resins, etc.), aliphatic polyamines and their copolymers, polycarbonates and Copolymers, polyphenylene sulfides and copolymers thereof, poly-Maple and copolymers thereof, polyethers And copolymers thereof, polyacid nitriles and copolymers thereof, polyether ketones and copolymers thereof, poly-__-types and copolymers thereof, polyketones and copolymers thereof, elastomers, liquid crystal polymers, etc. . These may be used alone or in combination of two or more. More preferably, the thermoplastic resin constituting the matrix component is made of polycarbonate 'polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, nylon. At least one selected from the group consisting of polypropylene, polyethylene, polyether ketone, polyphenylene sulfide, and acrylonitrile-butadiene-styrene copolymer resin. Moreover, examples of the thermosetting resin which can be used for the matrix include an epoxy resin, a thermosetting acrylic resin, a urethane resin, a polyoxyn resin, a phenol resin, a thermosetting modified PPE resin, and The thermosetting type PPE resin, the polyimine resin and the copolymer thereof, the aromatic polyamidimide resin, and the copolymer thereof may be used singly or in combination of two or more kinds. Further, 'the aromatic polyamine resin which can be used as a matrix' can be exemplified by an aromatic dicarboxylic acid component derived from terephthalic acid and/or isophthalic acid, and 1,4-phenylenediamine, 1> a group of 3_phenylenediamine, 3,4,-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and 13-bis(3-aminophenoxy)benzene A wholly aromatic polyamine selected from at least one aromatic diamine component. -25- 201118121 The rubber system which can be used for the substrate is not particularly limited, and there are natural NR), acrylic rubber, acrylonitrile butadiene rubber (NBR rubber pentadiene rubber (IR), urethane rubber, ethylene propylene EPM) ), epichlorohydrin rubber, chloroprene rubber (CR), rubber and copolymers thereof, styrene butadiene rubber (SBR), butadiene (BR), butyl rubber, and the like. The composition of the present invention is prepared by mixing insulative asphalt-based graphitization with a matrix, and when mixing, a kneading machine, each machine, a blending machine, a roll, an extruder, a honing machine, and a self-revolving type are suitably used. Stir the mixing device or mixing device. Here, when the matrix resin is thermosetting or rubber, the molding and hardening reaction can be carried out after the resin or rubber before the mixing and the insulating and the graphitized short fibers. In order to further increase the thermal conductivity of the thermally conductive composition of the present invention, a niobium other than the niobium carbide-coated pitch-based graphitized short fibers may be added, and examples thereof include oxides such as alumina, magnesia, cerium oxide, and zinc oxide. A metal hydroxide such as aluminum hydroxide or magnesium hydroxide, a metal nitride such as aluminum nitride, a metal oxygen such as aluminum oxide oxide, a metal carbide such as carbonitride, or a carbon material such as diamond. It is appropriate to add this to the function. In addition, it is also possible to use two or more types of the above-mentioned compounds, which are mostly larger than the pitch-based graphitized short fibers, and it is necessary to pay attention to the addition amount or the addition ratio. In addition, in the case of the addition of the material, it is necessary to maintain the insulating property. Therefore, in order to further improve the moldability, mechanical properties, and the like, it is also possible to add glass fiber or titanate rubber according to the required function. ( ), iso-rubber (polyoxadiene rubber short fiber type mixing machine, etc.) The pitch of the chemical tree is required. The metal boron nitride nitride can be used. However, with light weight and conductive K ° characteristics, Brassica -26· 201118121, zinc oxide whisker, shed aluminum whisker, boron nitride whisker, aromatic polyamide fiber, alumina fiber, carbonized cellulose fiber, asbestos fiber, gypsum fiber, etc. It is also possible to use more than two types of these. It is also possible to add sand such as limestone, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, and sour sand as needed. Non-fibrous materials such as carbonates such as acid salts, calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, glass flakes, and ceramic beads. These may also be hollow, and then Also Two or more types of these are used. However, most of the above-mentioned compounds are density-based pitch-based graphitized short fibers, and for the purpose of weight reduction, it is necessary to pay attention to the addition amount or the addition ratio. Additives are added to the composition. Examples of other additives include release agents, flame retardants, emulsifiers, softeners, plasticizers, and surfactants. More specifically, the use of the composition is described. A heat dissipating member, a heat transfer member, or a constituent material thereof for efficiently radiating heat generated by an electronic component such as a semiconductor element or a power source, such as a light source, in an electronic device or the like. The thermally conductive composition to be formed may be at least selected from the group consisting of an injection molding method, a press molding method, a calender molding method, a roll molding method, an extrusion molding method, a casting molding method, and a blow molding method. One of the methods is to form a molded body, and the sheet-like forming system can be formed by extrusion molding such as press-out of a roll, extrusion of a die, or the like. Depending on the forming method and the substrate, the molding can be carried out at a temperature higher than the melt viscosity of the resin. -27- 201118121 When the matrix is a thermally conductive composition made of a thermosetting resin, it can be used before curing. The resin is formed by molding, and can be formed by at least one selected from the group consisting of an injection molding method, a press molding method, a calender molding method, a roll molding method, an extrusion molding method, and a casting molding method. Molding conditions: The molding conditions depend on the forming method and the substrate, and may be a method of imparting a curing temperature to the resin, etc. during molding or in a suitable mold. When the matrix is thermally conductive by an aromatic polyamide resin In the case of the composition, the aromatic polyamide resin can be dissolved in a solvent, and the pitch-based graphitized short fibers are mixed therein and molded by a casting method. Here, as the solvent, if the aromatic polyamide resin is dissolved, It is not particularly limited, and specifically, a guanamine-based solvent such as hydrazine, dimethyl dimethyl acetamide or N-methylpyrrolidone can be used. When the matrix is a thermally conductive composition made of rubber, it can be molded by at least one of the methods selected from the group consisting of a press forming method, a calender molding method, and a roll forming method to obtain a molded body. The molding conditions depend on the forming method and the substrate, and a method of imparting a vulcanization temperature or the like to the rubber may be mentioned. A molding material such as a composite, a sheet, a grease or a lubricant, or a thermally conductive molded body can be obtained from the thermally conductive composition. The present invention comprises a molded body obtained from the above thermally conductive composition. EXAMPLES Examples are shown below, but the present invention is not limited thereto. Further, each of the oximes in the present embodiment was obtained by the following method. (1) Insulating asphalt-based graphitized short fibers and pitch-based graphitization -28- 201118121 The average fiber diameter of short fibers is determined according to 〖IS R7607, using a scale under an optical microscope to determine 60 pieces. Got it. (2) Insulating pitch-based graphitized short fibers and pitch-based graphitized short fibers The average number of fiber lengths was determined using SEI SHIN PIT A1, which was determined by an average of 1 500 pieces. (3) The crystallite size of the pitch-based graphitized short fiber was measured by the vibration method by the reflection of the (1 1 〇) plane appearing in the X-ray diffraction. (4) The end face of the pitch-based graphitized short fiber was observed by a transmission electron microscope at a magnification of 1,000,000 times, and was magnified 4 million times in the photograph to confirm the graphene sheet. In the observation of the fiber ends of the pitch-based graphitized short fibers, the end faces of the graphene sheets of 50 to 2.5 million times of the fiber ends of the five fibers were observed, and the full length A of the end faces of the graphene sheets at the ends of the fibers were measured ( The length B ( nm ) of the portion in which the end face is bent into a U shape, and the blocking ratio is obtained by the blocking ratio (%) = Β / Αχ 100. (5) The surface of the infiltrated pitch-based graphitized short fiber and the pitch-based graphitized short fiber was observed with a scanning electron microscope at a magnification of 2000 times to confirm defects and irregularities. (6) The coating amount of the hardened resin hardened resin of the infiltrated pitch-based graphitized short fiber is maintained at atmospheric temperature for 5 hours at 5 ° C to insulate the pitched graphitized short fiber by heating The specific resistance of the pitch-based graphitized short fibers in which the ytterbium (7) was insulated was calculated using the weight difference between the front and the back using the MCP-PD51 manufactured by Mitsubishi Chemical Corporation. (8) The specific resistance of the thermal conductive composition is obtained by using the technology Hiresta UP from the Mitsubishi Chemical Analysis Division -29-201118121. (9) The thermal conductivity of the thermally conductive composition was determined by using QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd. Reference Example 1 As the main raw material, pitch formed from a condensed polycyclic hydrocarbon compound was used. The optical anisotropy ratio is 100% and the softening point is 2 8 3 °c. Using a cap of a hole having a diameter of 0.2 mmφ, heated air was sprayed from the slit at a line speed of 5 500 m per minute, and the molten pitch was pulled to prepare a pitch-based short fiber having an average diameter of 1 1.2 μη. The spinning temperature at this time was 325 ° C and the melt viscosity was 17.5 Pa*S (175 poise). The spun fiber was added to the mat to form a mat, and the asphalt-based carbon fiber precursor web made of a pitch-based carbon fiber precursor having a basis weight of 35 Og/m2 was formed by cross-laying. The pitch-based carbon fiber precursor web was heated in air at 17 ° C at an average temperature increase rate of 5 ° C / min to 300 ° C without melting, and then calcined at 800 ° C. This pitch-based carbon fiber mesh cloth was pulverized at 900 rpm using a cutter (manufactured by TURBO Co., Ltd.), and graphitized at 3000 ° C. The average fiber diameter of the pitch-based graphitized short fibers was 8 · 1 μm, and the ratio of the fiber diameter dispersion to the average fiber diameter was (CV値) is 1 1%. The average fiber length is ΙΟΟμπι, and the crystal size from the growth direction of the hexagonal mesh surface is 8 Onm. The end faces of the pitch-based graphitized short fibers were observed by a transmission microscope to confirm that the graphene sheets were closed. The blocking ratio of the graphene sheets was 90.3%. Further, the surface was substantially smooth by the observation of the scanning electron microscope, "concavity -30-201118121". The specific resistance of the pitch-based graphitized short fibers is 2.5 χ1 〇·4 Ω·cm. Example 1 100 parts by weight of an epoxy resin main component (registered trademark "Epicoat 871" manufactured by Nippon Resin Co., Ltd.), 30 parts by weight, using a self-propelled mixer (registered trademark "Defoaming Rantaro ARV3 10" manufactured by THINKY Co., Ltd.) Epoxy resin hardener (registered trademark "Epicure FL240" manufactured by Nippon Resin Co., Ltd.) mixed with 20 parts by weight of pitch-based graphitized short fibers of Reference Example 1 and then filtered to remove excess hardening Resin. This was treated at 15 ° C for 2 hours to obtain an insulative pitch-based graphitized short fiber. Fig. 1 shows a scanning electron microscope observation photograph of the obtained insulating pitch-based graphitized short fibers. It was confirmed that the epoxy resin was coated on the surface of the graphitized short fibers. Concavities and bumps were not observed. The coating amount of the epoxy resin was 7.8 parts by weight with respect to 100 parts by weight of the pitch-based graphitized short fibers. The specific resistance of the insulative pitch-based graphitized short fiber was 5.0 x 10 08 Q.cm. The average pitch diameter of the insulative pitch-based graphitized short fibers was 9.8 μηι ′, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV値) was 12%. The number average fiber length is 100 μm. Example 2 90 parts by weight of an epoxy resin main component (registered trademark "Epicoat 806" manufactured by Nippon Resin Co., Ltd.) and 11 parts by weight of an epoxy resin hardener (曰-31 - 201118121 registered trademark of this epoxy resin) "Epicure YH3 07") parts and 2 parts by weight of epoxy resin hardening catalyst (product name "IMB II 02" made by Japanese epoxy resin) were dissolved in 200 parts by weight of ethyl methyl ketone, using a self-revolving mixer (The registered trademark "Defoaming Rantaro ARV310" manufactured by THINKY Co., Ltd.) was mixed with 30 parts by weight of the pitch-based graphitized short fibers prepared in Reference Example 1 for 3 minutes, and then filtered to remove excess resin before curing. This was treated at 150 k for 2 hours to obtain an insulative pitch-based graphitized short fiber. As a result of surface observation, it was confirmed that the epoxy resin was applied to the pitch-based graphitized short fibers. Concavities and bumps were not observed. The coating amount of the epoxy resin was 3.1 parts by weight with respect to 100 parts by weight of the pitch-based graphitized short fibers. The specific resistance of the insulative pitch-based graphitized short fibers was 7.10 Ω·cm. The insulating pitch-based graphitized short fibers had an average fiber diameter of 9.0 μm, and the fiber diameter dispersion to average fiber diameter ratio (CV値) was 11%. The average number of fibers is 1 〇〇 μιη. Example 3 90 parts by weight of an epoxy resin main component (registered trademark "Epicoat 806" manufactured by Nippon Resin Co., Ltd.) and 110 parts by weight of an epoxy resin curing agent (registered trademark "Epicure YH307" manufactured by Enamel Epoxy Co., Ltd.) 2 parts by weight of an epoxy resin hardening catalyst (registered trademark "IMB II 02" manufactured by Nippon Resin Co., Ltd.) was dissolved in 1 part by weight of ethyl methyl ketone, and was registered using a self-revolving mixer (THINKY company). The trademark "defoaming Rantaro ARV310") was mixed with 30 parts by weight of the pitch-based graphitized short fibers of Reference Example 1 for 3 minutes, and then filtered to remove excess resin before hardening. This will be painted on -32- 201118121. The Weiwei fiber short-termized ink stone stone system is the green leaching of the lipid-rich tree to the arsenic to the ring. When the time is OK, the fruit can be small. 2 The knot is mi 1 and the temperature is 0°. β sentence 0 0^ 察 oxygen ί 观 ring is short, seven, no one _ ΐ 而 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石The stone edge is the best for the blue. The amount of leaching, the weight Ω amount 8 7 4 &lj 01 is 10 times the coating phase of the ο m insulating asphalt-based graphitized short fiber having an average fiber diameter of 9.3 μm η fiber diameter dispersion versus average fiber The ratio of diameters (CV 値) is 11%. The average number of fibers is ΙΟΟμηι. Example 4 90 parts by weight of an epoxy resin main component (registered trademark "Epicoat 8 06" manufactured by Nippon Epoxy Resin Co., Ltd.), 110 weight, using a self-propelled mixer (registered trademark "Defoaming Rantaro ARV310" manufactured by THINK Co., Ltd.) Epoxy resin curing agent (registered trademark "Epicure YH3〇7", manufactured by Nippon Resin Co., Ltd.), 2 parts by weight of epoxy resin curing catalyst (registered trademark "IMBI102" manufactured by Japan Epoxy Resin Co., Ltd.) and 25 parts by weight The pitch-based graphitized short fibers prepared in Reference Example 1 were mixed for 3 minutes, and then filtered to remove excess resin before hardening. This was treated at 150 °C for 2 hours to obtain an insulated pitch-based graphitized short fiber. Fig. 2 shows a scanning electron microscope observation photograph of the obtained insulating pitch-based graphitized short fiber, and it was confirmed that the epoxy resin was coated on the surface of the graphitized short fiber, but the unevenness was observed on the coated surface. One. Defects were not observed. The epoxy resin coating amount was 9.2 parts by weight with respect to 1 part by weight of the pitch-based graphitized short fiber. Insulating asphalt-based graphitized staple fiber -33- 201118121 The specific resistance of the dimension is 3.〇xl01()n_cm. The insulating pitch-based graphitized short fibers had an average fiber diameter of 10.3 μm, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV値) was 11%. The average number of fibers is 1 〇 〇 μ m. Example 5 5 parts by weight of a two-liquid hardening type polyoxynoxy resin (trade name "SE 1 740A & B" manufactured by Toray Dow Polyoxane) was dissolved in 200 parts by weight of toluene, and a self-revolving mixer (THINKY) was used. The company-registered trademark "Defoaming Rantaro ARV310") was mixed with 100 parts by weight of the pitch-based graphitized short fibers prepared in Reference Example 1 for 3 minutes, and then toluene was volatilized. This was treated at 150 ° C for 2 hours to obtain an insulating pitch-based graphitized short fiber. As a result of the surface observation, it was confirmed that the coating of the pitch-based graphitized short fibers of the polysiloxane resin was not observed. The coating amount of the polyoxymethylene resin was 4.8 parts by weight with respect to 1 part by weight of the pitch-based graphitized short fibers. The specific resistance of the insulative pitch-based graphitized short fiber is 7.0 χ 107 Ω·£: πι. The insulating pitch-based graphitized short fibers had an average fiber diameter of 9.0 μm, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV 値) was 11%. The average number of fibers is ΙΟΟμηι. Example 6 2 parts by weight of an aromatic polyamine resin (registered trademark "Technora" manufactured by Teijin Technology Co., Ltd.) was dissolved in 200 parts by weight of Ν-methylpyrrolidine «% -34-201118121 ketone, using a self-revolving mixture. The machine (manufactured by INKY Co., Ltd., "Defoaming Rantaro ARV3 10") was mixed with 100 parts by weight of the reference example of the pitch-based graphitized short fibers to obtain a mixed slurry. This was dried in a rotary evaporator at 2 °C. The surface-treated pitch-based rayon short fibers obtained by dipping and drying the same amount of the aromatic polyamine resin solution were washed three times to obtain an insulating pitch-based graphitized short fiber. As a result of surface observation, the application of the aromatic polyamide resin to the pitch-based graphitized short fibers was confirmed. Concavities and bumps were not observed. The amount of the aromatic polyamine resin applied was 5.9 parts by weight with respect to 100 parts by weight of the pitch-based graphitized short fibers. Insulating bituminous ray The specific resistance of the inkized short fiber is 2.1x1 06 Ω·cm. The insulating pitch-based graphitized short fibers had an average fiber diameter of 9·0 μη, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV値) was 11%. The average number of fibers is ΙΟΟμπι. Example 7 100 parts by weight of an epoxy resin main component (registered trademark "Epicoat 871" manufactured by Sakamoto Epoxy Co., Ltd.), 30, was used in a revolving mixer (trademark "Defoaming Rantaro ARV3 10" manufactured by THINK Co., Ltd.). 100 parts by weight of a mixed solution of an epoxy resin curing agent (registered trademark "Epicure FL240", manufactured by Nippon Epoxy Co., Ltd.) and 1 part by weight of the insulating asphalt-based graphite prepared in Example 1 The staple fibers were mixed for 6 minutes to form a mixed slurry. This slurry was subjected to a pressurization process using a vacuum press (Beichuan Fine Mechanism) to obtain a flat composite material having a thickness of 〇5 mm, which was cured at 4 ° C for 4 - 35 to 2011 18121 hours to prepare a thermally conductive composition. The specific resistance of the thermally conductive composition was 8.5 χ 109 Ω. (The thermal conductivity of the thermal conductive composition was 6.2 W/(m, K). Example 8 Using a self-revolving mixer (trademark "THINKY Co., Ltd." ARV310"), 90 parts by weight of epoxy resin base agent (registered trademark "Epicoat 806" manufactured by Enamel Epoxy Co., Ltd.), and 110 parts by weight of epoxy resin hardener (registered trademark of Epoxy Resin, Japan) "), 100 parts by weight of a mixed solution of 2 parts by weight of an epoxy resin curing catalyst (trade name "IMBI1 02"), and 100 parts by weight of the insulative asphalt system prepared in Example 2 The graphitized short fibers were mixed for 6 minutes to form a mixed slurry, and the slurry was subjected to press working by a vacuum press (Beichuan Fine Mechanism) to obtain a flat composite material having a thickness of 〇5 mm, which was hardened at 150 ° C. A thermally conductive composition was prepared for 4 hours. The specific resistance of the thermally conductive composition was 6.5 Χ 107 Ω. (The thermal conductivity of the ηι» thermally conductive composition was 8.3 W/(m·K). Example 9 In addition to the insulating used Asphalt-based graphitized short fiber is made in Example 3. A thermally conductive composition was produced in the same manner as in Example 7. The specific resistance of the thermally conductive composition was 3.5 x 10 Ω·cm. The thermal conductivity of the thermally conductive composition was 7.3 W/(mK ). Example 1 〇μ - 36-201118121 A thermally conductive composition was produced in the same manner as in Example 7 except that the insulating pitch-based graphitized short fibers used were the same as in Example 4. The specific resistance of the thermally conductive composition was 7.2 X 1 0 1 1 Ω · cm. The thermal conductivity of the thermally conductive composition was 4.8 W / (m . K ). Example 1 1 Except that the insulating pitched graphitized short fibers used were the same as those of Example 5, and Example 7 The thermal conductivity of the composition was 7. 5 W 1 08 Ω ♦ cm. The thermal conductivity of the thermally conductive composition was 7. 1 W / ( m . K ). Example 1 2 The insulative pitch-based graphitized short fiber was formed into a thermally conductive composition in the same manner as in Example 7 except that the insulating layer was formed. The specific resistance of the thermally conductive composition was 1 · 0 χ 1 07 Ω · cm. The thermal conductivity of the material is 5.9 W / (m · K ). Example 1 3 Revolving mixer (THINKY defoaming ritaro ARV-310) '100 parts by weight of the reference example 1 made of pitch-based graphitized short fibers, 5 parts by weight of polyfluorene-oxygen resin (Dolly Dow Corning, SE1740), 300 parts by weight of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed for 3 minutes to form a composite slurry. This was spray-dried by a spray dryer (B-2000, manufactured by Shibata Scientific Co., Ltd.) to obtain insulation. The asphalt is a graphitized short fiber. Treatment temperature -37- 201118121 degrees is 200 °C. The insulating layer coating amount was 5 parts by weight with respect to 100 parts by weight of the pitch-based graphitized short fibers. The specific resistance of the insulative pitch-based graphitized short fibers was 5.0 x 12 〇 12 n.cm. The insulating pitch-based graphitized short fibers had an average fiber diameter of 8.5 μm and a ratio of fiber diameter dispersion to average fiber diameter (CV値) of 12%. The average number of fibers is ΙΟΟμιη. As a result of surface observation, the coating of the pitch-based graphitized short fibers by the polyoxyxylene resin was confirmed. Concavities and bumps are not observed. Example 1 4 Using a self-revolving mixer (manufactured defoaming ritaro ARV-310), 1 part by weight of the pitch-based graphitized short fiber and 2.25 parts by weight of an epoxy resin main agent were prepared. (Epcoat 8 06, a registered trademark of Japan Epoxy Resin), 2.75 parts by weight of an epoxy resin curing agent (Epicure 307, a registered trademark of Japan Epoxy Resin), and 0.05 part by weight of an epoxy resin hardening catalyst (Japan) The epoxy resin product name "IMBI102") and 300 parts by weight of ethyl methyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed for 3 minutes to form a composite slurry. This was spray-dried by a spray dryer (B-290, manufactured by Shibata Scientific Co., Ltd.) to obtain an insulative pitch-based graphitized short fiber. The treatment temperature was 200 °C. The insulating layer coating amount was 5 parts by weight with respect to 1 part by weight of the pitch-based graphitized short fiber. The specific resistance of the insulative pitch-based graphitized short fibers was 2.0 x 1012 Q.cm. £ -38- 201118121 Insulating pitch-based graphitized short fibers have an average fiber diameter of 8·5 μm. The ratio of fiber diameter dispersion to average fiber diameter (CV値) is 13%. The average fiber length is 1〇〇μηι. . As a result of surface observation, it was confirmed that the epoxy resin was applied to the pitch-based graphitized short fibers, and the number of irregularities was one, and the defects were one. Example 1 5 Using 100 parts by weight of the pitch-based graphitized short fiber of Reference Example 1 and 1.12 parts by weight of an epoxy resin main agent using a self-revolving mixer (manufactured defoaming Ryotaro ARV-3 10 ) (Epicoat 806, a registered trademark of Japan Epoxy Resin), 3.8 parts by weight of an epoxy resin curing agent (registered trademark "Epicure 307" manufactured by Nippon Resin Co., Ltd.), and 0.02 parts by weight of an epoxy resin curing catalyst (Japanese epoxy resin product name "IMB 1102"), 300 parts by weight of ethyl methyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed for 3 minutes to form a composite slurry. This was spray-dried by a spray dryer (B-2 90, manufactured by Shibata Scientific Co., Ltd.) to obtain an insulated pitch-based graphitized short fiber. The treatment temperature was 200 °C. The insulating layer coating amount was 2.5 parts by weight with respect to 1 part by weight of the pitch-based graphitized short fibers. The specific resistance of the insulative pitch-based graphitized short fiber is 8.9 χ 10 η Ω · (: πι. The average fiber diameter of the insulated pitch-based graphitized short fiber is 8.2 μm, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV 値) The average fiber length was 12 μτη. The results of surface observation confirmed that the epoxy resin was applied to the pitch-based graphitized short fibers, and the defect was 0, and the concave-39-201118121 was convex. 1 6 100 parts by weight of the pitch-based graphitized short fiber of Reference Example 1 and 5 parts by weight of tetraethoxysilane (Wako Pure Chemicals Co., Ltd.) using a self-revolving mixer (THINKY Defoaming Ryotaro ARV-310) 1 part by weight of 28% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), 300 parts by weight of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and 75 parts by weight of water were mixed for 3 minutes to form a composite slurry. A spray dryer (Shibata) Scientifically produced, B-2 90) spray-drying treatment to obtain insulated pitch-based graphitized short fibers at a treatment temperature of 130 ° C. Insulation relative to 100 parts by weight of bitumen-based graphitized short fibers The coating amount of the layer is 5 parts by weight. The specific resistance of the pitched graphitized short fibers is S.OxloHn.cm. The average pitch diameter of the insulative pitch-based graphitized short fibers is 8.6 μm, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV値) is 1. 2%. The average fiber length was 1 〇〇μηι. As a result of surface observation, it was confirmed that the polysiloxane gel film was applied to the pitch-based graphitized short fibers, and the number of defects was zero, and the number of irregularities was three. 7 Using a self-revolving mixer (de-foaming Ryotaro ARV-3 10 manufactured by THINKY), 45 parts by weight of the insulative pitch-based graphitized short fibers obtained in Example 13 and 100 parts by weight of polyoxynoxy resin ( Toray Dow Corning, SE1 740) was mixed for 3 minutes to become a composite slurry. The slurry was pressed and processed by a vacuum press (-40-201118121 Beichuan Precision Mechanism) to obtain a composite of thickness 〇5 mm. The molded body was formed into a heat conductive group at 13 (TC hardening for 2 hours. The specific resistance of the heat conductive composition was 3.5 X 1 〇 13 Ω · cm. The thermal conductivity of the heat conductive group was 4.9 W/(mK). Example 1 8 Using a self-propelled mixer (registered trademark of TH INKY Co., Ltd.) Taro ARV-310"), 45 parts by weight of the pitched graphitized short fibers obtained in Example 14 and 1 part by weight of polyoxyl resin, manufactured by Li Dow Corning, SE1 74 0), were mixed for 3 minutes. The composite slurry vacuum press (Beichuan Fine Mechanism) pressurizes the slurry to obtain a 0.5 mm flat composite molded body, which is cured at 130 ° C for 2 hours to form a thermally conductive composition. The specific resistance is LOxl 0 Ι 3 Ω · The thermal conductivity of the thermal conductivity composition is 4.7 W / (m_K). Example 1 Using 45 parts by weight of the pitched graphitized short fiber obtained in Example 15 and 1 part by weight of a blending machine (manufactured by THINKY Co., Ltd., "Ritaro ARV-3 10") Polyoxyl resin, manufactured by Li Dow Corning, SE1740), was mixed for 3 minutes, and a composite slurry vacuum press (Beichuan Fine Mechanism) was used to pressurize the slurry to obtain a 0.5 mm flat composite molded body. The thermosetting composition was cured at ° C for 2 hours. The specific resistance of the thermally conductive composition was 1.0 x 1 〇 13 Ω · The thermal conductivity of the thermally conductive composition was 4.8 W / ( ηη·Κ). Defoaming insulation of the flat product (East. Decomposing insulation by thickness in cm ° (East. Made with thickness -41 · 201118121 Example 20 using a self-revolving mixer (THINKY defoaming Rantaro ARV-310)' 4 parts by weight of the insulating pitched graphitized short fibers obtained in Example 16 were mixed with 100 parts by weight of polyoxynoxy resin (manufactured by Toray Dow Corning, SE1740) for 3 minutes to form a composite slurry. The press machine (Beichuan Precision Mechanism) pressurizes the slurry to obtain a flat composite molded body having a thickness of 0.5 mm, and is cured at 30 ° C for 2 hours to form a thermally conductive composition. Specific resistance of the thermally conductive composition 1 _ 0 X 1 0 13 Ω · cm. The thermal conductivity of the thermal conductive composition was 5.1 W/(mK). Comparative Example 1 Except that the insulating pitch-based graphitized short fibers used were those of Reference Example 1. A thermally conductive composition was produced in the same manner as in Example 6. The specific resistance of the thermally conductive composition was 6.0 X 1 0·1 Ω·cm. The thermal conductivity of the thermally conductive composition was 9.3 W/(m · K ). The possibility of utilizing the insulating asphalt of the present invention is short in graphitization Dimensional, by using a resin which does not have a melting point of 250 ° C or lower and whose precursor is liquid soluble in a solvent, and coating a pitch-based graphitized short fiber having excellent thermal conductivity, and exhibiting high heat conductivity at one side. Insulation is provided. In this way, it can be widely used in electronic devices and heat-dissipating members for electronic components that require high heat dissipation characteristics, and thermal management is made possible. 42- 201118121 [Simplified illustration] Figure 1 A scanning electron microscope observation photograph of the insulated pitch-based graphitized short fibers obtained in Example 1. Fig. 2 is a scanning electron microscope observation photograph of the insulated pitch-based graphitized short fibers obtained in Example 4.

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Claims (1)

201118121 七、申請專利範圍： 1. —種絕緣化之瀝青系石墨化短纖維，其特徵爲藉 由不具有250°C以下的熔點，且其前驅物爲液狀，或前驅 物或其本身爲可溶於至少1種類的溶劑中之樹脂，塗覆瀝 青系石墨化短纖維。 2. 如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維’其在掃描型電子顯微鏡中以800〜1 000倍所觀察的 影像之觀察視野中’每i條的凹凸及缺陷係丨〇個地方以下 ’或在以2000倍所觀察的影像之觀察視野中，每i條的凹 凸及缺陷係1 5個地方以下。 3 .如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維’其中該樹脂係熱硬化性樹脂❹ 4 ·如申請專利範圍第3項之絕緣化之瀝青系石墨化短 纖維’其中該熱硬化性樹脂係由環氧樹脂、胺基甲酸乙酯 樹脂、熱硬化性丙烯酸樹脂及聚矽氧樹脂所成之群選出的 至少一種之樹脂。 5 .如申請專利範圍第4項之絕緣化之瀝青系石墨化短 纖維，其中該熱硬化性樹脂係環氧樹脂。 6 ·如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維，其中該樹脂係由芳香族聚醯胺、芳香族聚醯亞胺及 脂肪族聚醯亞胺所成之群選出的至少一種。 7.如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維，其中相對於100重量份的該瀝青系石墨化短纖維而 言，用於塗覆的樹脂爲1〜10重量份。 -44- 201118121 8. 如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維，其中該瀝青系石墨化短纖維的比電阻爲1.0x1 〇6Ω . cm以上。 9. 如申請專利範圍第1項之絕緣化之瀝青系石墨化短 纖維，其中該瀝青系石墨化短纖維係以中間相瀝青當作原 料，平均纖維直徑爲2〜2〇nm，纖維直徑分散對平均纖維 直徑之百分率（CV値）爲3〜15%，個數平均纖維長爲20 〜5 00 μιη，來自六角網面的成長方向的雛晶尺寸爲3 Onm以 上，經透射型電子顯微鏡的塡料端面觀察中石墨烯薄片係 關閉，而且在掃描型電子顯微鏡的觀察表面係實質上平坦 〇 1 0 ·—種導熱性組成物，其係由如申請專利範圍第1 項之絕緣化之瀝青系石墨化短纖維與由熱塑性樹脂、熱硬 化性樹脂、芳香族聚醯胺樹脂及橡膠所成之群選出的至少 1種之基質成分所成，相對於100重量份的基質成分而言， 含有3〜3 00重量份的絕緣化之瀝青系石墨化短纖維。 1 1 ·如申請專利範圍第1 0項之導熱性組成物，其中構 成基質成分的熱塑性樹脂係由聚碳酸酯類、聚對苯二甲酸 乙二酯類、聚對苯二甲酸丁二酯類、聚2,6 -萘二甲酸乙二 酯類、尼龍類、聚丙烯類、聚乙烯類、聚醚酮類、聚苯硫 類、及丙烯腈-丁二烯-苯乙烯系共聚合樹脂類所成之群選 出的至少一種之樹脂。 1 2 .如申請專利範圍第1 〇項之導熱性組成物，其中構 成基質成分的熱硬化性樹脂係由環氧樹脂、熱硬化性丙烯 -45- 201118121 酸樹脂、胺 硬化型改性 脂及其共聚 之群選出的 1 3.如 成基質成分 烯腈丁二烯 基甲酸乙酯 膠、氯丁二 膠（SBR) 出的至少一 14.— 項之導熱性 基甲酸乙酯樹脂、聚矽氧樹脂類、酚 PPE樹脂、及熱硬化型PPE樹脂、聚 物、芳香族聚醯胺醯亞胺樹脂及其共 至少一種之樹脂。 申請專利範圍第1 〇項之導熱性組成物 的橡膠係由天然橡膠（NR)、丙烯酸 橡膠（NBR橡膠）、異戊二烯橡膠（ 橡膠、乙烯丙烯橡膠（EPM)、環氧 烯橡膠（CR)、聚矽氧橡膠、苯乙烯 、丁二烯橡膠（BR)、及丁基橡膠所 種。 種導熱性成形體，其係由如申請專利 組成物所得。 樹脂、熱 醯亞胺樹 聚物所成 ，其中構 橡膠、丙 IR)、胺 氯丙烷橡 丁二烯橡 成之群選 範圍第10 -46 -201118121 VII. Patent application scope: 1. An insulative pitch-based graphitized short fiber characterized by not having a melting point below 250 ° C, and the precursor is liquid, or the precursor or itself A resin soluble in at least one type of solvent, coated with pitch-based graphitized short fibers. 2. In the case of the insulative pitched graphitized short fiber of the first application of the patent scope, the observation and field of view of the image observed in a scanning electron microscope at 800 to 1,000 times Below or below one place, or in the observation field of the image observed at 2000 times, the unevenness and defects of each i are less than 15 places. 3. The asphalt-based graphitized short fiber of the insulating material of the first aspect of the patent application, wherein the resin is a thermosetting resin ❹ 4 · the insulating pitched graphitized short fiber of claim 3 The thermosetting resin is at least one selected from the group consisting of an epoxy resin, a urethane resin, a thermosetting acrylic resin, and a polyoxyxylene resin. 5. The insulating pitched graphitized short fiber of claim 4, wherein the thermosetting resin is an epoxy resin. 6. The asphalt-based graphitized short fiber insulated according to the first aspect of the patent application, wherein the resin is selected from the group consisting of aromatic polyamine, aromatic polyimine and aliphatic polyimine. At least one. 7. The insulative pitch-based graphitized short fiber of the first aspect of the invention, wherein the resin for coating is from 1 to 10 parts by weight based on 100 parts by weight of the pitch-based graphitized short fiber. -44- 201118121 8. The insulating pitched graphitized short fiber of claim 1, wherein the pitch-based graphitized short fiber has a specific resistance of 1.0 x 1 〇 6 Ω·cm or more. 9. Insulating pitched graphitized short fibers according to claim 1 of the patent scope, wherein the pitch-based graphitized short fibers are made of mesophase pitch as a raw material, the average fiber diameter is 2 to 2 〇 nm, and the fiber diameter is dispersed. The percentage of the average fiber diameter (CV値) is 3 to 15%, the average fiber length is 20 to 500 μm, and the crystallite size from the growth direction of the hexagonal mesh surface is 3 Onm or more, which is transmitted electron microscope. The graphene sheet is closed in the observation of the end surface of the tantalum, and the observation surface of the scanning electron microscope is substantially flat. The thermal conductive composition is an insulating asphalt as claimed in claim 1 The graphitized short fiber is formed of at least one type of matrix component selected from the group consisting of a thermoplastic resin, a thermosetting resin, an aromatic polyamide resin, and a rubber, and is contained with respect to 100 parts by weight of the matrix component. 3 to 30,000 parts by weight of the insulative pitch-based graphitized short fibers. 1 1 The thermally conductive composition of claim 10, wherein the thermoplastic resin constituting the matrix component is a polycarbonate, a polyethylene terephthalate or a polybutylene terephthalate. , poly 2,6-naphthalenedicarboxylate, nylon, polypropylene, polyethylene, polyether ketone, polyphenylene sulfide, and acrylonitrile-butadiene-styrene copolymer resin At least one resin selected from the group formed. The thermally conductive composition of the first aspect of the invention, wherein the thermosetting resin constituting the matrix component is an epoxy resin, a thermosetting propylene-45-201118121 acid resin, an amine hardening type modified grease, and The selected one of the copolymerized groups is as follows: 3. As the matrix component acrylonitrile butadiene carboxylate, chloroprene (SBR), at least one of the thermal conductive urethane resin, polyfluorene An oxyresin, a phenol PPE resin, and a thermosetting PPE resin, a polymer, an aromatic polyamidoximine resin, and at least one resin thereof. The rubber of the thermal conductive composition of claim 1 is made of natural rubber (NR), acrylic rubber (NBR rubber), isoprene rubber (rubber, ethylene propylene rubber (EPM), epoxy olefin rubber (CR). , a polyene oxide rubber, a styrene, a butadiene rubber (BR), and a butyl rubber. A thermally conductive shaped body obtained by the composition of the patent application. Made of rubber, propylene (IR), and chloropropane rubber butadiene rubber into the group of 10 - 46 -
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