201027565 六、發明說明： 【發明所屬之技術領域】 本發明係關於含有樹脂材料與碳纖維之導電性樹脂複 合材料。詳細而言’本發明係關於一種含有樹脂材料與碳 纖維之導電性材料’其特徵爲相較於過去之包含樹脂材料 與碳纖維之導電性樹脂複合材料，具有良好之導電性且亦 顯不加工成形時寺之優異物性’且碳纖維自該導電性樹脂 Φ 複合材之脫落性低。 【先前技術】 過去’由樹脂與導電性塡充劑所構成之導電性樹脂複 合材料被廣泛使用於半導體領域、電器設備相關領域、汽 車•航空領域。使用該等導電性樹脂複合材料之主要目的 舉例爲例如保護半導體零件免受靜電影響、阻斷電磁波以 防止精密設備之誤動作、防止因摩擦造成之靜電•發熱 ⑩ 等。 不過’對母材樹脂賦與導電性之方法爲於樹脂中添加 賦予離子傳導性之材料之方法，或於樹脂中添加例如金屬 微粒子、金屬纖維、碳微粒子、碳纖維（在高溫下使作爲 原料之丙烯酸纖維或瀝青（石油、石炭、焦碳等副產物）碳 化作成之PAN系碳纖維或PITCH系碳纖維。以下，於本 說明書中稱爲「通用碳纖維」）等導電性塡充劑之方法。 其中，就性能、環境問題等方面而言，使用碳系材料賦予 導電性已成爲主流。 -5- 201027565 然而’使用粒徑爲數微米之碳粒子作爲導電性塡充劑 以展現必要之導電性時’相對於1 0 〇質量份之樹脂有必要 添加40〜50質量份’即使是科琴黑亦需要添加8〜15質量 份。使用該等碳粒子之複合材’與原本樹脂相比，會引起 黏度上升•流動性下降、或硬度上升等物性變化。結果， 成爲成形加工時之模具轉印性下降、光澤等之外觀不良或 耐衝擊性降低之原因。 又使用如上述之通用碳纖維作爲導電性塡充劑時，相 對於樹脂1 00質量份以例如3 0質量份左右添加，亦可獲 得體積固有電阻102Qcm左右之導電性，但仍有因添加量 過多使流動性惡化之問題。 近年來，作爲此種導電性塡充劑，已成爲使用以碳奈 米管（以下亦稱爲「CNT」）等爲代表之纖維直徑〇.7~130nm 左右之微細碳纖維。微細碳纖維爲以電弧放電法或氣相成 長法等製造之基本上由連續之6員環碳構造所構成之使石 墨烯薄片成爲單層或多層之管狀結構者，纖維徑爲奈米等 級’長度爲微米等級，高的縱橫比爲其一特徵之導電性塡 充劑材料。已有報導若使用此微細碳纖維，由於其高的導 電性，藉由對樹脂100質量份添加數質量份即可獲得具有 所需導電性之樹脂複合材（專利文獻1、2)。 然而，由母材樹脂與此等微細碳纖維所構成之導電性 複合材料，由於樹脂中添加可賦予良好導電性之量的微細 碳纖維，而使破斷延伸率等之樹脂複合材的物性、成形性 降低。該等問題已成爲使用此樹脂複合材成形目的成形物 -6- 201027565 時之課題。又，微細碳纖維之纖維徑極細，亦有熔融樹脂 對碳纖維表面之濡濕性差等，而有發生微細碳纖維自所成 形之樹脂複合材脫落之傾向。此等導電性塡充劑之微細碳 纖維之脫落，尤其在半導體領域中，被視爲半導體製品故 障、損壞之原因。因此，要求有良好導電性、優良成形性 等之原本母材樹脂所具有之樹脂特性、進而碳纖維之低脫 落性任一者均可以達到充分程度之由樹脂與碳纖維所構成 0 之導電性樹脂複合材料。 另一方面，專利文獻3中提出包含纖維外徑分布不同 之二群以上之碳纖維之氣體貯藏材。若小的平均外徑之碳 纖維群與平均外徑比其大的碳纖維群組合時，可形成獲得 氣體吸附位置之最適細孔構造，可謂爲提高氣體貯藏量 者。 然而，專利文獻3中所示之氣體貯藏材並非是混練碳 纖維與樹脂材料而成者，因此並非提供導電性良好之樹脂 ❿ 材料。 又，專利文獻4提出於樹脂結合劑中含有第一石墨微 細纖維與比其更細徑之第二石墨纖維之導電性材料。 該專利文獻4中揭示之導電性材料係混練於酚系樹脂 結合劑者’溶劑亦爲必要。再者所使用之石墨微細纖維爲 混合平均直徑5〜20nm者與平均直徑3 00nm~1 000nm者。 又’專利文獻5中提出混合碳纖維之平均直徑較大者 與較小者而成之導電性組成物。 然而’專利文獻5之碳纖維爲平均直徑13μπι者與平 201027565 均直徑7μιη者’係通用碳纖維。 [先前技術文獻] [專利文獻] [專利文獻1]特開2006-306960號公幸g [專利文獻2]特開2006-225648號公報 [專利文獻3]特開2〇〇5·ΐ85951號公報 [專利文獻4]特開平8-222025號公報 [專利文獻5]特開平5-32819號公報 【發明內容】 [發明欲解決之課題][Technical Field] The present invention relates to a conductive resin composite material containing a resin material and carbon fibers. In detail, the present invention relates to a conductive material containing a resin material and a carbon fiber, which is characterized in that it has good electrical conductivity and is not formed into a shape as compared with a conductive resin composite material containing a resin material and a carbon fiber in the past. The excellent physical properties of the temple are low and the carbon fibers are less detachable from the conductive resin Φ composite. [Prior Art] In the past, conductive resin composite materials composed of a resin and a conductive chelating agent have been widely used in the fields of semiconductors, electrical equipment, and automobiles and aviation. The main purpose of using such a conductive resin composite material is, for example, to protect semiconductor parts from static electricity, to block electromagnetic waves to prevent malfunction of precision equipment, and to prevent static electricity and heat generation due to friction. However, the method of imparting conductivity to the base material resin is a method of adding a material imparting ion conductivity to the resin, or adding, for example, metal fine particles, metal fibers, carbon fine particles, and carbon fibers to the resin (it is used as a raw material at a high temperature). A method of using a conductive enthalpy such as a PAN-based carbon fiber or a PITCH-based carbon fiber in which acrylic fibers or pitch (such as petroleum, charcoal, and coke) are carbonized. Hereinafter, it is referred to as "general carbon fiber" in the present specification. Among them, in terms of performance, environmental problems, and the like, the use of a carbon-based material to impart conductivity has become mainstream. -5- 201027565 However, when using carbon particles having a particle diameter of several micrometers as a conductive chelating agent to exhibit the necessary conductivity, it is necessary to add 40 to 50 parts by mass relative to the resin of 10 parts by mass. Qinhe also needs to add 8 to 15 parts by mass. The composite material using these carbon particles causes a change in physical properties such as an increase in viscosity, a decrease in fluidity, and an increase in hardness as compared with the original resin. As a result, the mold transfer property at the time of molding processing is lowered, the appearance of gloss or the like is poor, and the impact resistance is lowered. When a general-purpose carbon fiber as described above is used as the conductive entanglement agent, it is added in an amount of, for example, about 30 parts by mass based on 100 parts by mass of the resin, and conductivity of about 102 Qcm in volume specific resistance can be obtained, but the amount of addition is too large. The problem of deteriorating liquidity. In recent years, fine carbon fibers having a fiber diameter of about 7 to 130 nm, which are represented by carbon nanotubes (hereinafter also referred to as "CNT"), have been used as the conductive enthalpy. The fine carbon fiber is a tubular structure in which a graphene sheet is formed into a single layer or a plurality of layers, which is basically composed of a continuous 6-membered ring carbon structure, which is manufactured by an arc discharge method or a vapor phase growth method, and has a fiber diameter of a nanometer' length. It is a micro-scale, high aspect ratio of its characteristic conductive squeegee material. It has been reported that a resin composite material having desired conductivity can be obtained by adding several parts by mass to 100 parts by mass of the resin by using the fine carbon fiber (Patent Documents 1 and 2). However, the conductive composite material composed of the base material resin and the fine carbon fibers is formed by adding fine carbon fibers in an amount capable of imparting good conductivity to the resin, and the physical properties and formability of the resin composite material such as elongation at break are obtained. reduce. These problems have been the subject of the use of the molded article for molding of the resin composite material -6- 201027565. Further, the fine carbon fibers have a very fine fiber diameter, and the wet resin has poor wettability to the surface of the carbon fibers, and the fine carbon fibers tend to fall off from the formed resin composite. The shedding of the fine carbon fibers of these conductive chelating agents, especially in the field of semiconductors, is considered to be the cause of malfunction and damage of semiconductor products. Therefore, it is required that any of the resin properties of the original base material resin having good electrical conductivity and excellent moldability, and further the low resilience of carbon fibers, can be achieved by compounding a conductive resin composed of a resin and a carbon fiber to a sufficient extent. material. On the other hand, Patent Document 3 proposes a gas storage material comprising two or more carbon fibers having different fiber outer diameter distributions. If a small carbon fiber group having a small average outer diameter is combined with a carbon fiber group having a larger average outer diameter, an optimum pore structure for obtaining a gas adsorption position can be formed, which is an increase in gas storage amount. However, the gas storage material shown in Patent Document 3 is not a kneading carbon fiber and a resin material, and therefore does not provide a resin ruthenium material having good conductivity. Further, Patent Document 4 proposes a conductive material containing a first graphite fine fiber and a second graphite fiber having a smaller diameter than the resin binder. It is also necessary that the conductive material disclosed in Patent Document 4 is kneaded in a phenol-based resin binder. Further, the graphite fine fibers used are those having a mixed average diameter of 5 to 20 nm and an average diameter of 300 nm to 1 000 nm. Further, Patent Document 5 proposes a conductive composition in which the average diameter of the mixed carbon fibers is larger and smaller. However, the carbon fiber of Patent Document 5 is a general-purpose carbon fiber of an average diameter of 13 μm and a flat of 201027565 and a diameter of 7 μm. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2006-225648 [Patent Document 2] JP-A-2006-225648 (Patent Document 3) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. 5-32819
本發明之課題係提供一種包含樹脂材料與碳纖維之新 穎導電性樹脂複合材料。尤其本發明之課題爲提供一種一 方面維持良好之導電性’另一方面改善與成形性相關之破 斷延伸率’且降低碳纖維自樹脂複合材脫落之導電性樹脂 複合材料。 [解決課題之手段] 本發明者等爲解決上述課題而進行積極檢討之結果， 發現碳纖維之平均纖維外徑超過20nm且爲3 00nm以下， 且包含纖維外徑分布不同之至少二群碳纖維群調配於樹脂 材料中之導電性樹脂複合材料顯示良好之導電性，且亦改 善成形時之破斷延伸率，又亦降低該碳纖維自該導電性樹 脂複合材料之脫落。另外，平均外徑在20nm至300nm之 -8 - 201027565 碳纖維之工業生產之例較少，本發明藉由開發平均外徑在 20nm〜300nm範圍之碳纖維之製造技術，立意混合在該範 圍內之纖維外徑分布不同之二群碳纖維群而完成者。亦即 本發明具有以下之構成。 一種導電性樹脂複合材料，其係包含母材樹脂及碳纖 維之導電性樹脂複合材料’其特徵爲該碳纖維之平均纖維 外徑超過20nm且爲3 00nm以下，且包含纖維外徑分布不 φ 同之至少二群碳纖維’且相對於該母材樹脂100質量份， 含有1〜11.2質量份之碳纖維。 本發明進一步顯示前述之導電性樹脂複合材料者，其 中前述纖維外徑分布不同之至少二群碳纖維群區分爲平均 纖維外徑較細之碳纖維群A與較粗之碳纖維群b時，以質 量比計，該碳纖維群B比該碳纖維群A大，且令該碳纖維 群A之平均纖維外徑爲a，令該碳纖維群b之平均纖維外 徑爲b時，a/b之比率成爲0.8以下。 參 本發明進一步顯示前述之導電性樹脂複合材料者，其 中前述碳纖維群A之平均外徑a超過20nm且爲丨00nm以 下’碳纖維群B之平均纖維外徑b超過l〇〇nm且爲3〇〇nm 以下’且二者在母材樹脂中實質上經混合而均質化。An object of the present invention is to provide a novel conductive resin composite material comprising a resin material and carbon fibers. In particular, it is an object of the present invention to provide a conductive resin composite material which maintains good electrical conductivity while improving the breaking elongation associated with formability and reducing the loss of carbon fibers from the resin composite. [Means for Solving the Problems] The inventors of the present invention conducted a positive review to solve the above problems, and found that the average fiber outer diameter of the carbon fibers exceeds 20 nm and is 300 nm or less, and at least two carbon fiber group blends having different fiber outer diameter distributions are found. The conductive resin composite material in the resin material exhibits good electrical conductivity, and also improves the breaking elongation at the time of molding, and also reduces the peeling of the carbon fiber from the conductive resin composite material. In addition, the average outer diameter is between 20 nm and 300 nm -8 - 201027565. The industrial production of carbon fiber is less. The invention develops the fiber in the range by developing a carbon fiber manufacturing technology with an average outer diameter of 20 nm to 300 nm. Completion of two groups of carbon fiber groups with different outer diameter distributions. That is, the present invention has the following constitution. A conductive resin composite material comprising a base resin and a carbon fiber conductive resin composite material, wherein the carbon fiber has an average fiber outer diameter of more than 20 nm and 300 Å or less, and includes a fiber outer diameter distribution not being the same as At least two carbon fibers 'and 1 to 11.2 parts by mass of carbon fibers are contained with respect to 100 parts by mass of the base resin. The present invention further shows the above-mentioned conductive resin composite material, wherein at least two groups of carbon fiber groups having different outer diameter distributions of the fibers are classified into a carbon fiber group A having a finer outer diameter outer diameter and a coarser carbon fiber group b, and mass ratio The carbon fiber group B is larger than the carbon fiber group A, and the average fiber outer diameter of the carbon fiber group A is a, and when the average fiber outer diameter of the carbon fiber group b is b, the ratio of a/b is 0.8 or less. Further, the present invention further shows the above-mentioned conductive resin composite material in which the average outer diameter a of the carbon fiber group A exceeds 20 nm and is 丨00 nm or less. 'The average fiber outer diameter b of the carbon fiber group B exceeds 10 nm and is 3 〇. 〇 nm or less 'and both are homogenized by substantially mixing in the base resin.
本發明另顯示前述之導電性樹脂複合材料者，g φ M 述碳纖維群A之質量存在比小於碳纖維群B之質量存在 比。 本發明進一步顯示前述之導電性樹脂複合材料者，其 中前述碳纖維爲藉由氣相成長法製造之碳纖維。 -9 - 201027565 本發明另爲前述之導電性樹脂複合材料，其中前述碳 纖維係形成三次元網絡狀之碳纖維構造體，且該碳纖維構 造體具有將複數個粒狀部相互以碳纖維立體地結合而成之 網絡構造。 本發明爲進一步顯示前述之導電性樹脂複合材料者， 其中前述粒狀部具有上述碳纖維之平均纖維外徑之1.3倍 以上之相當於圓之平均外徑。 本發明爲另顯示前述之導電性樹脂複合材料者，其中 上述導電性樹脂複合材料之破斷延伸率爲4 0%以上。 本發明另爲則述之導電性樹脂複合材料，其中使用前· 述導電性樹脂複合材料成形之成形物表面電阻値爲 103〜1012Ω/〇。 [發明效果] 本發明之導電性樹脂複合材料爲藉由將上述說明之碳 纖維調配於樹脂中，而具有優異之導電性' 改善之破斷延 伸率、及碳纖維不容易脫落之特性者。藉由該等特性，導 電性樹脂複合材料對應於廣泛之成形條件，且其成形之抗 裂性優異，因此可提供可適用於寬廣用途之導電性材料。 該用途例示爲例如個人電腦、筆記型電腦、遊戲機（家庭 用遊戲機、業務用遊戲機、小鋼珠台及吃角子老虎等）、 顯示器裝置（LCD、有機EL、電子紙、電漿顯示器及投影 機等）、輸電零件（以感應線圈式輸電裝置之外殼爲代表）。 又，作爲該用途，例如可例示爲印表機、影印機、掃描機 -10- 201027565 及傳真機（包含該等之複合機）。進而，作爲該用途，可例 示爲VTR照相機、光學薄膜式照相機、數位靜態照相 機、照相機用之透鏡單元、防盜裝置及行動電話等之精密 機器。尤其本發明之導電性樹脂複合材料適用於照相機鏡 筒 '如數位照相機之數位圖像資料處理裝置之框體、外殼 以及框。 此外’本發明導電性樹脂複合材料亦適用於按摩機或 ❷ 高氧治療器等之醫療設備；錄像機（所謂DVD錄影機等）、 視聽設備及電子樂器等之家庭電器製品；小鋼珠台或吃角 子老虎等遊戲裝置；以及搭載有精密感測器之家庭用遙控 器等之零件。 又本發明之導電性樹脂複合材料可利用於各種車輛零 件、電池、發電裝置、電路基板、積體電路之模具、光碟 基板、匣市磁碟、光學卡、1C記億卡、連接器、電纜耦合 器、電子零件之運送用容器（IC卡槽箱、矽晶圓容器、玻 φ 璃基板收納容器、磁頭托盤、及載帶等）、抗靜電用或靜 電去除零件（電子照相感光裝置之帶電輥等），以及各種機 構零件（包含齒輪、轉盤、轉子及螺絲等，包括微型設備 用機構零件）。 【實施方式】 以下，依據較佳實施形態詳細說明本發明。 本發明爲將纖維外徑分布不同之至少二群碳纖維群混 練於樹脂材料而成之樹脂成形體。纖維外徑分布不同之碳 -11 - 201027565 纖維群較好經分別的製造，隨後，混練於樹脂材料中。混 合碳纖維可在粉體之階段混合，亦可個別添加於樹脂中混 練後混合。 本發明中使用之碳纖維只要是使用如上述之纖維外徑 分布不同之至少二群碳纖維者即無特別限制，但以組合其 平均外徑超過20nm且爲1 OOnm以下者作爲平均外徑較小 的碳纖維群，及其平均外徑超過lOOnm且爲3 00nm以下 者作爲平均外徑較大的碳纖維群，且使二者實質混合均質 化而成之混合物較佳。混合二者時，可保持比僅平均外徑 較小的碳纖維群或僅平均外徑較大的碳纖維群單獨使用時 更爲良好之導電性，另一方面可改善與成形性有關之破斷 延伸率，且可減少碳纖維自樹脂複合材之脫落。 此處所用之平均纖維外徑係以倍率設定成35000倍之 掃描型電子顯微鏡，對測定對象之碳纖維，隨機拍攝複數 個視野，以測定至少3視野以上且纖維外徑之測定點數合 計超過5 0點之方式測定各攝影視野中全部可測定之纖維 外徑，且將其數平均者。本發明之導電性樹脂複合材料中 使用之碳纖維於該方法每一視野中可測定20〜50點之纖維 外徑。 通常，添加碳纖維所成之樹脂成形體之導電性、黏 度、斷裂係受到碳纖維之外徑影響者。由於外徑愈細則每 單位添加之條數愈增加故而導電性有提高之傾向。又黏度 有外徑愈細愈高之傾向。就用途而言，黏度愈高則愈不容 易發揮樹脂本來之物性。關於碳纖維之製造成本，外徑愈 -12- 201027565 細則每單位質量之製造成本愈高。因此，本發明爲著眼於 藉由混練碳纖維外徑不同者，可同時發揮碳纖維外徑較細 者之性質，與較粗者之性質之優異性質而完成本發明者。 例如，於具有該平均外徑之碳纖維群A中混入具有比 其大之平均外徑之碳纖維群B時，碳纖維群B處於單獨粗 略分散於母材樹脂基質中之複合狀態，可藉由碳纖維群A 之碳纖維埋入碳纖維群B之碳纖維與樹脂間之空間，據 φ 此’藉由增加電接觸而提高導電性。又，藉由於碳纖維群 B分散間隙間分散碳纖維群A之碳纖維，而使碳纖維絡 合，亦爲可增大破斷延伸率等力學強度者（圖1)。 高分子材料之破壞機構係由加工條件及基本構造決 定。又’亦會因結晶化度、構造之均勻性、配向性、晶球 之大小及其分布、分子鏈之長度與其分布等之結晶性、材 料傷痕、切入等物理缺陷之存在而變化。例如，如圖1所 示，於表面有切入傷痕之情況，裂痕會沿著非結晶樹脂構 φ 成之分子鏈界面傳播。如圖1所示，添加碳纖維時，由於 斷裂應力由具有架橋效果之碳纖維所承受，使裂痕之傳播 速度變慢，因此可提高破斷延伸率。 纖維爲較微細程度時，由於纖維表面與樹脂之接觸面 增大’使剪斷應力分散，故而纖維不容易自樹脂拉出。然 而，纖維直徑愈細，成本亦較高，且亦難以分散。因此， 本發明係藉由使細徑之碳纖維分散於粗徑之碳纖維之四 週，因此即使使用少量之細徑碳纖維，亦可維持優異之導 電性，且具有提高破斷延伸率之效果。 -13- 201027565 又’本發明中使用之碳纖維較好爲平均纖維外徑超過 20nm且爲30〇nm以下，而爲三次元網絡狀之構造體。該 碳纖維構造體爲其特徵係以複數延伸出該碳纖維之狀態， 具有使該碳纖維彼此結合之粒狀部之碳纖維構造體。該等 碳纖維構造體並沒有特別的限制，而可藉由化學氣相成長 法製造。再者，若平均外徑超過3 OOnm則每單位量之條數 降低，因此較好使用平均外徑300nm以下者。 再者，本發明之導電性複合材料中，上述纖維外徑分 布不同之至少二群碳纖維群之調配比例，相較於使用單獨 碳纖維群，只要可獲得更具有上述導電性提高、破斷延伸 率提高、進而纖維脫落減少之效果，則沒有特別限制，但 區分爲平均纖維外徑較細之碳纖維A與較粗之碳纖維B之 情況，以質量比計，該碳纖維B大於碳纖維A，且令該碳 纖維A之平均纖維外徑爲a，令該碳纖維B之平均纖維外 徑爲b時，大致上區分成a/b比率爲0.8以下，更好爲 0.07-0.8，又更好爲0.2〜0.8左右者較佳。以該等調配比 例，可期待特別優異之效果。 具有如上述網絡構造之氣相碳纖維構造體進而較好爲 具有如下特徵之碳纖維構造體：具有複數之粒狀部，該複 數之粒狀部之自各粒狀部分別獨立延伸出複數之上述碳纖 維使整體呈現出三次元之擴展’且自其一個粒狀部延伸出 之複數氣相碳纖維之至少一部份亦與其他粒狀部結合之樣 態，而至少部份具有該氣相碳纖維之三次元網絡狀構造。 又，本說明書中，所謂自粒狀部位使碳纖維「延伸 14- 201027565 出」，主要意指粒狀部位之複數碳纖維並非是由其他結合 劑（包含碳物質者）僅在外觀上呈連結狀態，而是成爲如上 述之碳結晶構造性結合，亦即粒狀部係與上述碳纖維藉由 共有相同多層構造之石墨稀（graphene)薄片而連結之狀 態。 另外，本說明書中所謂的「整體呈現出三次元擴展」 意指複數條碳纖維自一位置之粒狀部以彼此獨立之方向延 0 伸出，且該延伸出之樣態係以粒狀部做爲基點，在立體空 間內使複數纖維伸長之構造。 至於該等碳纖維構造體更好爲連結二個該粒狀部之碳 纖維之平均長度爲3·0~20.0μιη者。 又，上述所謂的「兩個粒狀部間之距離」意指自碳纖 維所伸長之一個粒狀部連結至鄰接之粒狀部之碳纖維長 度。該鄰接之粒狀部間之距離爲測定自一個粒狀體之中心 部至鄰接之粒狀部中心部之距離者。粒狀體間之平均距離 φ 未達〇·5μιη時，由於碳纖維之長度不足而無法充分延伸擴 展，例如分散調配於母材樹脂中時，會有無法形成良好導 電通路之虞，另一方面，平均距離超過100 μιη時，該碳纖 維之構造體會成爲比較大的碳纖維構造體，分散調配於母 材樹脂中時，成爲黏度升高之要因，因而有碳纖維集合體 相對於母材樹脂之分散性下降之顧慮。又，更適當之粒狀 部間之平均距離較好爲2.0〜50μιη，更好爲3.0〜20μηι左 右。 又，本發明中使用之碳纖維以該纖維外徑（nm)之分布 -15- 201027565 之標準偏差在25~40者較佳，最好爲30~40。使用標準偏 差在25〜40之碳纖維之導電性樹脂複合材料顯示3 0%以上 之破斷延伸率，若爲標準偏差爲3 0〜40之碳纖維則顯示 5 0%以上之破斷延伸率。此係認爲於採用本發明較好使用 之如上述三次元網狀結構體之碳纖維中，以該標準偏差範 圍所規定之纖維外徑之不均範圍中的粗纖維外徑之碳纖維 與細纖維外徑之碳纖維，對使用該碳纖維之導電性樹脂複 合材料之破斷延伸率施加互補之效果之故。 又在本申請案中，二個碳纖維群以外，亦可藉由添加 碳黑等其他塡充劑而強化導電性或力學特性。 具有上述平均纖維外徑及纖維外徑分布之標準偏差値 之碳纖維，於碳纖維之製造方法中，若爲批量式，則可爲 在1次製造反應中所獲得之碳纖維，若爲連續反應，則可 使能夠獲得適當製造量的1個連續期間作1次獲得之碳纖 維，或者亦可爲如此獲得之碳纖維之複數次量之混合物。 進行該混合時，使碳纖維群A與碳纖維群B實質混合均質 化成爲混合物，該混合物中源自碳纖維群B之碳纖維之質 量存在比大於源自碳纖維群A之碳纖維質量存在比之碳纖 維混合物亦較好可滿足上述平均纖維外徑與纖維外徑分布 之標準偏差範圍。 又，本發明中使用之較適用之碳纖維，對於上述三次 元網絡狀之構造體來說，並非單純的分歧構造，而是至少 部份具有該碳纖維之網絡狀構造，該碳纖維構造具有複數 之粒狀部，自該粒狀部延伸出複數條具有比各粒狀部之相 -16- 201027565 當於圓之平均外徑更細之纖維徑之碳纖維之樣態，且該粒 狀部係在該碳纖維之成長過程中形成者。複數碳纖維之結 合部之該粒狀部由於亦具有與如上述碳纖維相同之石墨烯 薄片之多層構造，因此能使碳纖維彼此強固地結合。因 此，對於更強固結合所期望之粒狀部之相當於圓之平均外 徑爲碳纖維之平均纖維外徑之1.3倍以上，更好爲1.5〜5.0 倍。藉由使強固的碳纖維如此強固地結合形成三次元網絡 φ 狀之碳纖維構造體，即使以混練等添加於樹脂中亦得以維 持該構造體，一般認爲該三次元網絡狀之立體構造與比碳 纖維外徑大之粒狀部，於導電性樹脂複合材之樹脂之基質 中可發揮物理性定錨效果，且可減少該碳纖維自該導電性 樹脂複合材脫落。 又，本說明書中所謂的「粒狀部之相當於圓之平均外 徑」爲測定對氣相碳纖維相互結合點之粒狀部所觀察之面 積，作爲一個真圓求得之直徑之値。具體而言，係以電子 φ 顯微鏡等，對氣相碳纖維相互結合點的粒狀部之外形進行 攝影，在該攝影圖像中，使用適當之圖像分析軟體，例如 WinRoof (商品名，三谷商事股份有限公司製造）描出各 粒狀部之輪廓，求出輪廓內之面積，基於該面積而計算出 各粒狀部之相當於圓之直徑，並加以平均而得者。 上述三次元網絡狀之碳纖維構造體以面積基準之相當 於圓之平均直徑較好爲20〜ΙΟΟμιη。此處所謂面積基準之 相當於圓之平均直徑係使用電子顯微鏡等對碳纖維構造體 之外形加以攝影，使用適當圖像解析軟體，例如 -17- 201027565Further, in the above-described conductive resin composite material, the mass ratio of the carbon fiber group A of g φ M is smaller than that of the carbon fiber group B. The present invention further shows the above-mentioned conductive resin composite material, wherein the carbon fiber is a carbon fiber produced by a vapor phase growth method. -9 - 201027565 The present invention is the conductive resin composite material described above, wherein the carbon fiber is formed into a three-dimensional network-like carbon fiber structure, and the carbon fiber structure has a plurality of granular portions which are three-dimensionally bonded to each other by carbon fibers. Network structure. The present invention is to further show the conductive resin composite material described above, wherein the granular portion has 1.3 times or more the outer diameter of the average fiber of the carbon fiber and corresponds to an average outer diameter of the circle. The present invention further provides the conductive resin composite material described above, wherein the conductive resin composite material has a breaking elongation of 40% or more. Further, in the conductive resin composite material described above, the surface resistivity of the molded article formed by using the conductive resin composite material described above is 103 to 1012 Ω/〇. [Effect of the Invention] The conductive resin composite material of the present invention is characterized in that it has an excellent conductivity-improved breaking elongation and a carbon fiber which is not easily peeled off by blending the carbon fiber described above with a resin. With such characteristics, the conductive resin composite material has a wide range of molding conditions and is excellent in crack resistance of the molding, so that a conductive material which can be applied to a wide range of applications can be provided. The use is exemplified by, for example, a personal computer, a notebook computer, a game machine (a home game machine, a business game machine, a small steel ball table, a slot machine, etc.), a display device (LCD, an organic EL, an electronic paper, a plasma display, and the like). Projector, etc., transmission parts (represented by the casing of the induction coil type power transmission device). Moreover, as such a use, for example, a printer, a photocopier, a scanner -10- 201027565, and a facsimile machine (including such a multifunction peripheral) can be exemplified. Further, as such a use, a precision machine such as a VTR camera, an optical film camera, a digital still camera, a lens unit for a camera, an antitheft device, and a mobile phone can be exemplified. In particular, the conductive resin composite material of the present invention is suitable for use in a camera lens, such as a frame, a casing and a frame of a digital image data processing device of a digital camera. In addition, the conductive resin composite material of the present invention is also suitable for medical equipment such as a massage machine or a high-oxygen therapeutic device; a household electrical appliance such as a video recorder (so-called DVD recorder, etc.), an audio-visual equipment, and an electronic musical instrument; A game device such as a slot machine; and a home remote controller equipped with a precision sensor. Further, the conductive resin composite material of the present invention can be used for various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk substrates, Bengbu magnetic disks, optical cards, 1C card, connectors, and cables. Couplings, containers for transporting electronic components (IC card slots, wafer containers, glass substrate storage containers, head trays, carrier tapes, etc.), antistatic or static electricity removal parts (electrophotographic photosensitive devices are charged) Rolls, etc., and various mechanical parts (including gears, turntables, rotors, and screws, including mechanical parts for micro devices). [Embodiment] Hereinafter, the present invention will be described in detail based on preferred embodiments. The present invention is a resin molded body obtained by kneading at least two groups of carbon fiber groups having different fiber outer diameter distributions to a resin material. Carbon with different outer diameter distribution of fibers -11 - 201027565 The fiber groups are preferably separately manufactured and then kneaded in a resin material. The mixed carbon fibers may be mixed at the stage of the powder, or may be separately added to the resin and mixed and mixed. The carbon fiber used in the present invention is not particularly limited as long as it has at least two groups of carbon fibers having different outer diameter distributions of fibers as described above, but the average outer diameter is more than 20 nm and is not more than 100 nm. The carbon fiber group and the carbon fiber group having an average outer diameter of more than 100 nm and not more than 300 nm are preferably a mixture of carbon fibers in which the average outer diameter is large, and the mixture is substantially mixed and homogenized. When mixing the two, it is possible to maintain a better electrical conductivity than a carbon fiber group having only a small average outer diameter or a carbon fiber group having a large average outer diameter alone, and on the other hand, it is possible to improve the fracture elongation associated with formability. Rate, and can reduce the shedding of carbon fiber from the resin composite. The average fiber outer diameter used here is a scanning electron microscope set at a magnification of 35,000 times, and a plurality of fields of view are randomly taken for the carbon fibers to be measured, and at least three fields of view are measured, and the total number of measurement points of the fiber outer diameter exceeds 5 The OD diameter of all measurable fibers in each photographic field of view was measured at 0 o'clock, and the number was averaged. The carbon fiber used in the conductive resin composite of the present invention can measure the fiber outer diameter of 20 to 50 points in each field of view of the method. Usually, the conductivity, viscosity, and fracture system of the resin molded body obtained by adding carbon fibers are affected by the outer diameter of the carbon fibers. As the outer diameter is increased, the number of added per unit is increased, and the conductivity tends to increase. The viscosity has a tendency to be finer and finer. In terms of use, the higher the viscosity, the less the resin's original physical properties can be easily exhibited. Regarding the manufacturing cost of carbon fiber, the outer diameter is -12- 201027565 The higher the manufacturing cost per unit mass. Therefore, the present invention has been made in view of the fact that by mixing the outer diameters of the carbon fibers, the inventors can simultaneously exhibit the properties of the outer diameter of the carbon fibers and the superior properties of the thicker ones. For example, when a carbon fiber group B having an average outer diameter larger than the carbon fiber group B having the average outer diameter is mixed, the carbon fiber group B is in a composite state in which the carbon fiber group B is roughly dispersed in the matrix of the base material resin, and the carbon fiber group can be used. The carbon fiber of A is buried in the space between the carbon fiber of the carbon fiber group B and the resin, and the electric conductivity is improved by increasing electrical contact. Further, since the carbon fibers are dispersed in the carbon fiber group B to disperse the carbon fibers of the carbon fiber group A, the carbon fibers are complexed, and the mechanical strength such as the breaking elongation can be increased (Fig. 1). The destruction mechanism of polymer materials is determined by the processing conditions and basic structure. Furthermore, it also changes due to the presence of physical defects such as crystallinity, material scar and cut-in, such as crystallinity, uniformity of structure, orientation, size and distribution of crystal spheres, length and distribution of molecular chains. For example, as shown in Fig. 1, in the case where the surface has a cut-in flaw, the crack propagates along the molecular chain interface formed by the amorphous resin structure φ. As shown in Fig. 1, when the carbon fiber is added, since the fracture stress is absorbed by the carbon fiber having a bridging effect, the propagation speed of the crack is slowed, so that the elongation at break can be improved. When the fiber is fine, the contact surface of the fiber surface and the resin is increased to disperse the shear stress, so that the fiber is not easily pulled out from the resin. However, the finer the fiber diameter, the higher the cost, and the more difficult it is to disperse. Therefore, in the present invention, by dispersing the carbon fibers having a small diameter in four weeks of the carbon fibers having a large diameter, even if a small amount of the fine carbon fibers are used, excellent electrical conductivity can be maintained and the elongation at break can be improved. Further, the carbon fiber used in the present invention is preferably a three-dimensional network-like structure in which the average fiber outer diameter exceeds 20 nm and is 30 Å or less. The carbon fiber structure is a carbon fiber structure having a granular portion in which the carbon fibers are bonded to each other in a state in which the carbon fibers are extended in a plurality. These carbon fiber structures are not particularly limited, and can be produced by a chemical vapor phase growth method. Further, if the average outer diameter exceeds 3,000 nm, the number of units per unit amount is lowered. Therefore, those having an average outer diameter of 300 nm or less are preferably used. Further, in the conductive composite material of the present invention, the blending ratio of at least two groups of carbon fiber groups having different outer diameter distributions of the fibers is improved as compared with the use of a single carbon fiber group, and the above-mentioned conductivity is improved and the elongation at break is obtained. The effect of increasing and further reducing the fiber shedding is not particularly limited, but is divided into a case where the carbon fiber A having a finer outer diameter of the fiber is smaller than the carbon fiber B having a larger outer diameter, and the carbon fiber B is larger than the carbon fiber A by mass ratio, and The average fiber outer diameter of the carbon fiber A is a, and when the average fiber outer diameter of the carbon fiber B is b, it is roughly divided into an a/b ratio of 0.8 or less, more preferably 0.07-0.8, and even more preferably 0.2 to 0.8. Better. With such a blending ratio, a particularly excellent effect can be expected. The carbon fiber structure having the network structure as described above is further preferably a carbon fiber structure having a plurality of granular portions, and the plurality of granular portions independently extend from the respective granular portions to form the plurality of carbon fibers. The entirety exhibits a three-dimensional extension' and at least a portion of the plurality of vapor-phase carbon fibers extending from one of the granules is also combined with other granules, and at least a portion of the three-dimensional element of the gas-phase carbon fiber Network structure. In the present specification, the term "extending 14-201027565" from the granular portion means that the plurality of carbon fibers in the granular portion are not connected by the other bonding agents (including the carbonaceous material) only in appearance. On the other hand, the carbon crystal is structurally bonded as described above, that is, the granular portion and the carbon fibers are connected by a graphite sheet having the same multilayer structure. In addition, the term "three-dimensional expansion as a whole" in the present specification means that a plurality of carbon fibers extend from a position of the granular portion in a direction independent of each other, and the extended state is made of a granular portion. As a base point, a structure in which a plurality of fibers are elongated in a three-dimensional space. As for the carbon fiber structures, it is preferable that the average length of the carbon fibers connecting the two granular portions is 3·0 to 20.0 μm. Further, the above-mentioned "distance between two granular portions" means the length of carbon fibers which are bonded from one granular portion elongated by the carbon fibers to the adjacent granular portions. The distance between the adjacent granular portions is measured from the center portion of one granular body to the distance from the center portion of the adjacent granular portion. When the average distance φ between the granules is less than 〇·5 μm, the length of the carbon fibers is insufficient to extend the expansion sufficiently. For example, when dispersed in the base resin, there is a possibility that a good conductive path cannot be formed. When the average distance exceeds 100 μm, the carbon fiber structure becomes a relatively large carbon fiber structure, and when dispersed and blended in the base resin, the viscosity is increased, and thus the dispersibility of the carbon fiber aggregate with respect to the base resin decreases. Concerns. Further, the average distance between the more appropriate granules is preferably from 2.0 to 50 μm, more preferably from 3.0 to 20 μm. Further, the carbon fiber used in the present invention has a standard deviation of the outer diameter (nm) of the fibers of -15 to 201027565 of preferably from 25 to 40, more preferably from 30 to 40. The conductive resin composite material having a standard deviation of 25 to 40 carbon fibers showed a breaking elongation of 30% or more, and a carbon fiber having a standard deviation of 30 to 40 showed a breaking elongation of 50% or more. This is considered to be the carbon fiber and the fine fiber of the outer diameter of the coarse fiber in the uneven range of the outer diameter of the fiber specified by the standard deviation range in the carbon fiber such as the above-mentioned three-dimensional network structure which is preferably used in the present invention. The carbon fiber of the outer diameter exerts a complementary effect on the breaking elongation of the conductive resin composite material using the carbon fiber. Further, in the present application, in addition to the two carbon fiber groups, conductivity or mechanical properties may be enhanced by adding other chelating agents such as carbon black. The carbon fiber having the above-mentioned average fiber outer diameter and the standard deviation of the fiber outer diameter distribution ,, in the method for producing carbon fibers, if it is a batch type, it may be a carbon fiber obtained in a single production reaction, and if it is a continuous reaction, It is possible to obtain a carbon fiber obtained once in one continuous period of a suitable production amount, or a mixture of a plurality of times of the carbon fiber thus obtained. When the mixing is carried out, the carbon fiber group A and the carbon fiber group B are substantially mixed and homogenized into a mixture in which the mass of the carbon fibers derived from the carbon fiber group B is greater than the carbon fiber mixture having a mass ratio greater than that of the carbon fiber group A derived from the carbon fiber group A. The standard deviation range of the above average fiber outer diameter and fiber outer diameter distribution can be satisfied. Further, the carbon fiber which is preferably used in the present invention is not a simple divergent structure for the three-dimensional network structure, but has at least a part of a network structure of the carbon fiber, and the carbon fiber structure has a plurality of particles. a portion in which a plurality of carbon fibers extending from the granule portion have a fiber diameter smaller than an average outer diameter of the circle, and the granule portion is The formation of carbon fiber in the process of growth. Since the granular portion of the junction of the plurality of carbon fibers also has a multilayer structure of the same graphene sheet as the above carbon fibers, the carbon fibers can be strongly bonded to each other. Therefore, the average outer diameter of the equivalent circle of the desired granular portion for stronger bonding is 1.3 times or more, more preferably 1.5 to 5.0 times, the outer diameter of the average fiber of the carbon fiber. By forming a strong carbon fiber so strongly to form a carbon fiber structure of a three-dimensional network φ shape, the structure can be maintained even if it is added to the resin by kneading or the like, and the three-dimensional network-like three-dimensional structure and carbon fiber are generally considered to be considered. The granular portion having a large outer diameter can exhibit a physical anchoring effect in the matrix of the resin of the conductive resin composite, and can reduce the loss of the carbon fiber from the conductive resin composite. In addition, the "average outer diameter corresponding to a circle of the granular portion" in the present specification is a diameter obtained by measuring the area observed by the granular portion of the gas-phase carbon fiber joint point as a true circle. Specifically, the shape of the granular portion of the junction of the vapor phase carbon fibers is photographed by an electron φ microscope or the like, and an appropriate image analysis software such as WinRoof (trade name, Mitani Corporation) is used in the photographed image. (manufactured by Co., Ltd.) The outline of each granular portion is drawn, and the area within the outline is obtained. Based on the area, the diameter of the corresponding circle of each granular portion is calculated and averaged. The above-mentioned three-dimensional network-like carbon fiber structure preferably has an average diameter of 20 to ΙΟΟμηη on the basis of the area. Here, the area reference is equivalent to the average diameter of the circle, and the shape of the carbon fiber structure is photographed using an electron microscope or the like, and an appropriate image analysis software is used, for example, -17- 201027565
WinRoof(商品名，三谷商事股份有限公司製造），描繪該 攝影圖像中各碳纖維構造體之輪廓，求得輪廓內面積，計 算各纖維構造體之相當於圓之直徑，且將其平均化者。該 相當於圓之平均直徑係成爲判斷經調配於樹脂之基質中時 的該碳纖維構造體之纖維長度的要因。槪述之，若相當於 圓之平均直徑未達2 0 μιη，則纖維長度短，有使用其之樹 脂複合材料無法獲得良好導電性之虞，另一方面，若爲超 過1 00 μιη者，則有例如藉由混練等而調配入樹脂基質中時 會產生較大之黏度上升，混合分散困難或者成形性劣化之 虞。 進而’上述三次元網絡狀之碳纖維構造體由於上述構 造而具有碳纖維以疏鬆狀態存在之蓬鬆構造，具體而言， 其鬆密度較好爲0.001~0.05g/cm3，更好爲0.001〜〇.〇2g/Cm3。 若鬆密度超過〇.〇5g/cm3，則少量添加難以改善樹脂之物 性。WinRoof (trade name, manufactured by Mitani Co., Ltd.), and draws the outline of each carbon fiber structure in the photographic image, calculates the inner area of the contour, calculates the diameter of the corresponding circle of each fiber structure, and averages it. . The average diameter corresponding to the circle is a factor for determining the fiber length of the carbon fiber structure when it is formulated in a matrix of the resin. As described above, if the average diameter of the equivalent circle is less than 20 μm, the fiber length is short, and the resin composite material using the same cannot obtain good conductivity. On the other hand, if it is more than 100 μm, For example, when it is blended into a resin matrix by kneading or the like, a large viscosity rise occurs, and mixing and dispersion are difficult or the formability is deteriorated. Further, the above-mentioned three-dimensional network-like carbon fiber structure has a bulky structure in which carbon fibers are present in a loose state due to the above structure, and specifically, the bulk density is preferably 0.001 to 0.05 g/cm3, more preferably 0.001 to 〇. 2g/Cm3. If the bulk density exceeds 〇.〇5g/cm3, it is difficult to improve the physical properties of the resin by a small amount of addition.
又’上述三次元網絡狀之碳纖維構造體爲於三次元網 絡狀中存在之碳纖維在其成長過程中形成之粒狀部彼此結 合’最好爲碳纖維構造體之佔有立體空間內具有複數個如 上述之粒狀部’於該立體空間內存在之碳纖維於其成長過 程中於所形成之粒狀部上相互結合，故雖如上述構造體本 身之電特性等亦極爲優異，但例如在一定壓縮密度 〇.8g/cm3下測定之粉體電阻値爲〇〇25ω· cm以下，更好 爲〇·〇〇5~0.020Ω · cm。此係因若粉體電阻値超過 0.025Ω · cm，則與樹脂複合材化時，難以製造良好之導電 -18- 201027565 性複合材料。 又’上述三次元網絡狀之碳纖維構造體由於具有高強 度及導電性，故構成碳纖.維之石墨烯薄片中缺陷少較佳， 具體而言，例如以雷曼分光分析法測定之ID/IG比在0.2 以下’更好在0.1以下者較佳。其中，雷曼分光分析中大 的單結晶石墨僅出現i 5 80cm·1附近之高峰（G帶）。由於結 晶爲有限微小尺寸或晶格缺陷，而出現1 3 6 OcnT 1附近之 φ 峰（D帶）。因此，D帶與G帶之強度比（R = I136g/I158G = Id/IG) 若在如上述特定値以下，則可認爲於石墨烯薄片中之缺陷 量少。 此處所謂之缺陷，係指由於在構成中間體之石墨烯薄 片之排列中侵入作爲雜質之不要原子、或者必要之碳原子 不足、又或者產生偏移而產生的石墨烯薄片之排列之不完 全部分（晶格缺陷（lattice defect))等。 再者，雖未特別限制，但上述三次元網絡狀之前述碳 φ 纖維在空氣中之燃燒起始溫度宜爲700°C以上，更好爲 7 5 0~900°C。如上述之三次元網絡狀碳纖維由於爲缺陷少 且碳纖維具有所期望之外徑者，因此成爲具有此種高熱安 定性者。 本發明之上述碳纖維集合體之比表面積較好爲10〜60 m2/g。比表面積若大如60m2/g以上時，碳纖維之外徑變 細，而變得難以分散等。另一方面，比表面積若爲1 〇m2/g 以下，則每單位量之碳纖維條數極少，故若少量添加難以 獲得高導電性之複合材料。 -19- 201027565 具有上述特徵之碳纖維構造體並沒有特別限制’但可 例如下列般調製。 基本上，以過渡金屬超微粒子作爲觸媒以CVD法化 學熱分解烴等有機化合物，獲得纖維構造體（以下稱爲中 間體），且使之再經高溫熱處理。 至於原料有機化合物可使用苯、甲苯、二甲苯等烴、 一氧化碳（C0)、乙醇等醇類等。雖未特別限制，但就獲得 本發明之纖維構造體而言，較好使用至少兩種以上分解溫 度不同之碳化合物作爲碳源。又，本說明書中所述之所謂 「至少兩種以上之碳化合物」未必爲使用兩種以上者作爲 必要之原料有機化合物，亦包含即使使用一種作爲原料有 機化合物之情況下，在纖維構造體之合成反應過程中，亦 會發生例如甲苯或二甲苯之加氫脫院化（hydrodealkylation) 等之反應，而於隨後之熱分解反應系統中成爲分解溫度不 同之兩種以上碳化合物之樣態者。 又，熱分解反應系統中存在如此之兩種以上碳化合物 作爲碳源時，各碳化合物之分解溫度不僅隨碳化合物之種 類而變動，亦隨原料氣體中各碳化合物之氣體分壓及莫耳 比而變動，因此藉由調整原料氣體中兩種以上之碳化合物 之組成比，可使用比較多的組合作爲碳化合物。 例如，以自甲烷、乙烷、丙烷類' 丁烷類、戊烷類、 己烷類、庚烷類、環丙烷、環己烷等烷類及環烷類，尤其 是碳數1~7左右之烷類；乙烯、丙烯、丁烯類、戊烯類、 庚烯類、環戊烯等烯類及環烯類，尤其是碳數1〜7左右之 -20- 201027565 烯類；乙炔、丙炔等炔類，尤其是碳數1~7 苯、甲苯、苯乙烯、二甲苯、萘、甲基萘' 族及雜芳香族烴，尤其是碳數6〜18左右之 香族烴；甲醇、乙醇等醇類，尤其是碳數 類；其他之一氧化碳、酮類、醚類等中選擇 化合物在期望之熱分解反應溫度區域中可發 度之方式調整氣體分壓、組合使用，及/或 φ 度區域中調整滯留時間，使其混合比最適化 地製造纖維集合體（中間體）。 此等兩種以上碳化合物之組合中，例如 合中’以甲院/本之莫耳比爲1〜6 0 0 ^較好爲 好爲3〜100較適宜。又，該値爲反應爐入口 比，例如，使用甲苯作爲碳源之一時，考慮 甲苯100%分解，以1:1產生甲烷及苯，則 以其他途徑供給即可。例如，甲烷/苯之莫ΐ Φ 相對於1莫耳之甲苯，添加2莫耳之甲烷即 此般相對於甲苯，其添加之甲烷方面，未必 備新鮮之甲烷之方法，亦可利用藉由循環使 排出之排出氣體中所含未反應之甲烷。 藉由使組成比在該範圍內，而可獲得具 部及粒狀部之任一種均十分發達之三次元網 構造體（中間體）。 另外，未必加以限定，但作爲控制纖維 要因列舉如下： 左右之炔類； 茚、菲等芳香 芳香族及雜芳 1~7左右之醇 之兩種以上碳 揮不同分解溫 可在特定之溫 而可效率良好 甲烷與苯之組 ,1.1 〜200，更 處之氣體組成 到在反應爐內 不足量之甲烷 Ϊ比爲3時， 可。再者，如 僅利用另外準 用自該反應爐 有微細碳纖維 絡構造之纖維 外徑之粗細之 21 - 201027565 1) 原料中烴化合物之濃度 2) 原料中之烴化合物與觸媒金屬之濃度比率 3) 於反應爐內之滞留時間。 欲使碳纖維之外徑粗大，只要提高原料中之烴化合物 濃度即可。又’原料中烴化合物與觸媒金屬之濃度比率， 爲使外徑某程度變粗大，就烴化合物與觸媒金屬之莫耳比 而目’係使觸媒金屬之莫耳比僅稍高即可。化學氣相成長 法（CVD法）中以觸媒金屬作爲核，亦較好使金屬觸媒增量 以進一步使碳纖維成長。 另外，氛圍氣體可使用氬氣、氦氣、氙氣等惰性氣體 或氫。 另外’作爲觸媒’係使用鐵、鈷、鉬等過渡金屬或二 茂鐵、乙酸金屬鹽等過渡金屬化合物與硫或噻吩、硫化鐵 等硫化合物之混合物。 中間體之合成可使用通常所進行的烴等之CVD法。 使特定調配比之成爲原料之煙及觸媒之混合液蒸發，將氯 氣等作爲載氣而導入反應爐內，於800〜1300 °C之溫度下 進行熱分解。藉此’合成複數個碳纖維構造體（中間體）集 合而成之數公分至數十公分大小之集合體，該碳纖維構造 體具有外徑爲100〜300 nm之纖維相互之間藉由以上述觸 媒之粒子作爲核而成長之粒狀體而結合的疏鬆之三次元結 構。 包含上述反應爐之製造裝置並未特別限制，但可例示 具有例如圖2中所示構造之製造裝置。圖中所示之製造裝 -22- 201027565 置1係使原料蒸發，使氣化之原料與載氣混合，將該原料 混合氣體導入反應爐8內部，在反應爐8內製造碳纖維 者°製造裝置1具備有充塡原料之原料槽2與進行原料之 輸送及朝反應爐8導入之載氣之氣體槽4，該等原料槽2 及氣體槽4係通過原料導入管3及氣體導入管5分別連接 於蒸發器6。進而，蒸發器6係通過原料混合氣體導入管 7連接於反應爐8。並且，於內部製造碳纖維之反應爐8 φ 使其形成爲圓筒狀，且在以其軸心方向之一端爲上端上， 具備將輸送之原料混合氣體導入反應爐8內部之導入噴嘴 9。另外’反應爐8之外周部設置作爲加熱機構1 1之加熱 器’自反應爐8之外周部加熱反應爐8內部。接著，以反 應爐8之軸心方向之另一端作爲下端側連接有儲存並回收 所製造之碳纖維之碳纖維回收器12。於該碳纖維回收器 12連接有排出氣體之氣體排出管13。 成爲原料之烴之熱分解反應主要係在觸媒粒子乃至於 φ 以該觸媒粒子作爲核而成長之粒狀體表面上發生，且因分 解產生之碳的再結晶化自該觸媒粒子乃至於粒狀體以一定 方向進行，而成長成纖維狀。然而，就獲得上述般之碳纖 維之較佳三次元網絡狀之碳纖維構造體而言，刻意改變該 等熱分解速度與成長速度之均衡，例如使用如上述之分解 溫度不同之至少兩種以上之碳化合物作爲碳源，使碳物質 非僅以一次元方向成長，而是以粒狀體爲中心使碳物質朝 三次元生長。不過，該等三次元碳纖維之成長並非僅依存 於熱分解速度與成長速度之均衡，亦受觸媒粒子之結晶面 -23- 201027565 選擇性、反應爐內之滯留時間、爐內溫度分布等之影響， 且，上述熱分解反應與成長速度之均衡不僅受如上述之碳 源種類之影響，亦受反應溫度及氣體溫度等之影響，但槪 言之，若成長速度比如上述之熱分解速度更快，則碳物質 成長成纖維狀，另一方面，若熱分解速度比成長速度快， 則碳物質於觸媒粒子之周面方向成長。因此，藉由刻意改 變熱分解速度及成長速度之均衡，可使如上述碳物質之成 長方向不成爲一定方向，而在控制下以多方向，形成本發 明之三次元構造者。再者，生成之中間體中，爲使纖維彼 此藉粒狀體結合而容易地形成如前述之三次元構造，較好 使觸媒等之組成、在反應爐內之滯留時間、反應溫度、及 氣體溫度等最適化。 再者，作爲效率良好地製造纖維構造體（中間體）之方 法，除使用使如上述般之分解溫度不同之兩種以上之碳化 合物爲最適混合比之方法以外，亦可舉出將供給於反應爐 之原料氣體於該供給口附近產生亂流之方法。此處所謂的 亂流係指激烈紊亂之氣流，指呈旋渦狀流動之氣流。 反應爐中，將原料氣體自其供給口導入反應爐內後， 立即藉由原料混合氣體中作爲觸媒之過渡金屬化合物之分 解而形成金屬觸媒微粒子，但其亦係經歷以下之階段。亦 即，首先，使過渡金屬化合物分解成爲金屬原子，接著， 藉由複數個，例如約100個原子左右之金屬原子之衝突引 起群集（cluster)生成。於該生成之群集之階段，不發揮作 爲纖維構造體（中間體）之觸媒之作用，藉由生成之群集彼 -24- 201027565 此之衝突進一步集合，成長成約3nm〜ΙΟηιη左右之金屬之 結晶性粒子’被用以作爲碳纖維構造體（中間體）之製造用 之金屬觸媒微粒子。 於該觸媒形成過程中，若如上所述存在由激烈之亂流 引起之渦流，則可能進行比僅作布朗運動之金屬原子或者 群集相互之間的碰撞更激烈之碰撞，藉此，隨著每單位時 間之碰撞次數之增加，短時間內以高產率獲得金屬觸媒微 φ 粒子，又，因渦流而使濃度、溫度等均勻化，藉此可獲得 粒子之尺寸一致的金屬觸媒微粒子。進而，於形成金屬觸 媒微粒子之過程中，藉由因渦流而引起之激烈碰撞，形成 金屬之結晶性粒子大量集合而成的金屬觸媒微粒子之集合 體。如此，金屬觸媒微粒子快速生成，碳化合物分解反應 位置的金屬觸媒表面之面積變大，因此，促進碳化合物之 分解，且充分供給碳物質，以上述集合體之各自之金屬觸 媒微粒子爲核，使碳纖維呈放射狀地成長，另一方面，若 〇 如上所述一部分碳化合物之熱分解速度快於碳物質之成長 速度，則碳物質亦於觸媒粒子之周面方向成長，於上述集 合體之周圍形成粒狀部，高效率地形成具有所需三次元結 構之纖維構造體（中間體）。再者，一般認爲前述金屬觸媒 微粒子之集合體中亦包括一部分活性低於其他觸媒微粒子 或者在反應途中失去活性之觸媒微粒子，一般亦認爲係於 凝集爲集合體之前在上述觸媒微粒子之表面成長、或者於 形成集合體之後以上述觸媒微粒子爲核進行成長而成非纖 維狀或者極短之纖維狀碳物質藉由存在於集合體之周緣位 -25- 201027565 置而形成前驅物之粒狀部者。因此’前述粒狀部由複數個 氣相碳纖維之端部及使碳物質僅於周面方向成長的金屬觸 媒微粒子所構成，且使氣相碳纖維彼此結合而成之粒狀部 分多形成複數個球體狀結構物之集合•集積態樣，而非單 純之球形，由於在如此狀態下碳物質進一步繼續成長，故 而與後述之退火處理互起作用，而在粒狀部集合·集積之 複數個氣相碳纖維之端部或複數個球狀結構物鄰接者形 成·共有連續的石墨烯薄片狀層，結果形成以粒狀部使複 數個氣相碳纖維彼此牢固結合之三次元網絡狀之氣相碳纖 維構造體。 於反應爐之原料氣體供給口附近，投入之原料氣體之 溫度較好爲3 5 0〜450 °C。原料氣體之流動產生亂流之具體 手段並沒有特別限定者，例如可採用使原料氣體以旋流導 入反應爐內之方法’或於可干擾自原料氣體供給口導出至 反應爐內之原料氣體之氣流的位置設置某種碰撞部等的方 法。作爲上述碰撞部之形狀，並無任何限定，若爲因以碰 撞部爲起點所產生之渦流而使反應爐內形成充分之亂流者 即可’例如可採用將各種形狀之隔板、槳、錐管、傘狀體 等以單獨或者組合複數個而配置1個乃至複數個之形態。 圖2例示之製造裝置1中，其例爲在導入噴嘴9周圍 設置整流·緩衝板10。整流•緩衝板爲配置在導入噴嘴9 附近’使原料混合氣體之流通受到阻礙而成爲衝突起點之 障礙物，藉由該障礙物與原料混合氣體進行衝突而產生渦 流’使溫度分布與濃度分布均勻化成爲可能。整流•衝突 -26 - 201027565 板之形狀並沒有任何限制’只要以整流•緩衝板作爲起點 產生之渦流不消滅且逐次形成至反應爐8之下端側之形狀 即可。 使觸媒及烴之混合氣體在設定爲8 00~ 13 00。(：範圍之溫 度下加熱生成而獲得之中間體，具有由碳原子所成之碎片 狀薄片貼附而成之不完全構造。若該中間體進行雷曼分光 分析’則D帶非常大即缺陷多。又，生成之中間體含有未 φ 反應原料、非纖維狀碳化物、焦油（tar)成分及觸媒金屬。 因此，爲了自此等中間體去除該等殘留物而獲得缺陷 少之所需碳纖維構造體，而以適當方法於2400〜3000 t：之 高溫進行熱處理。 亦即，例如使該中間體在800〜1 200°C下加熱去除未反 應原料或焦油成分等揮發分後，在2400〜3000。(：之高溫下 經退火處理藉此調製所需之構造體，同時使纖維中所含觸 媒金屬蒸發去除。又，此時，亦可在惰性氣體氛圍中添加 φ 還原氣體或微量一氧化碳氣體以保護物質構造。 若使上述中間體在2400〜300CTC範圍之溫度下進行退 火處理’則由碳原子所成之碎片狀薄片可分別結合形成複 數個石墨烯薄片狀之層，獲得期望之碳纖維。 另一方面，在製造本發明之導電性樹脂複合材料上可 使用之樹脂並沒有特別限制，舉例爲例如環氧樹脂、酣樹 月旨、聚胺基甲酸醋樹脂、三聚氰胺樹脂、尿素樹脂、苯胺 樹脂、呋喃樹脂、醇酸樹脂、二甲苯樹脂、不飽和聚醋樹 脂、二芳基苯二甲酸酯樹脂等硬化性樹脂、聚對苯二甲酸 -27- 201027565 丁二酯樹脂、聚對苯二甲酸乙二酯樹脂、聚碳酸酯、聚氧 化苯、聚苯基醚、尼龍6、尼龍66、尼龍12、聚乙縮醛、 聚乙烯、聚丙烯、聚丁二烯、聚丙烯腈、聚苯乙烯、聚甲 基丙烯酸甲酯、聚環氧乙烷、聚環氧丁烷、熱可塑性聚胺 基甲酸酯、苯氧樹脂、聚醯胺、乙烯/丙烯共聚物、乙烯 /1-丁烯共聚物、乙烯/丙烯/非共軛二烯共聚物、乙烯/丙烯 酸乙酯共聚物、乙烯/甲基丙烯酸縮水甘油酯共聚物、乙 烯/乙酸乙烯酯/甲基丙烯酸縮水甘油酯共聚物、乙烯/丙 烯-g-馬來酸酐共聚物、聚酯聚醚彈性體、聚四氟乙烯、纖 維素乙酸酯、乙基纖維素、聚二甲基矽氧烷、聚甲基丙烯 酸甲酯、聚乙酸乙烯酯、聚乙烯醇、聚氯化乙烯、聚乙烯 基吡咯啶、蔗糖八乙酸酯、聚苯乙烯、丙烯腈/ 丁二烯/苯 乙烯樹脂、聚氯化乙烯、丙烯腈/苯乙烯樹脂、甲基丙烯 酸樹脂、氯化乙烯、聚醯胺、聚乙縮醛' 改質之聚苯基 醚、聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、超高分 子量聚乙烯、聚苯基硫醚、聚醯亞胺、聚醚醯亞胺、聚丙 嫌酸酯、聚碾、聚醚颯、聚醚醚酮、液晶聚合物、聚四氟 乙烯及該等之改質物等熱可塑性樹脂。該等樹脂可爲均聚 物亦可爲共聚物，亦可爲兩種以上之混合物。 將上述碳纖維添加混合於上述樹脂中，形成本發明之 導電性樹脂複合材料。該導電性樹脂複合材料中之碳纖維 之調配量’相對於樹脂1〇〇質量份，上述碳纖維較好爲 1〜1〗.2質量份’更好爲3~7.7質量份。添加混合該所需量 之碳纖維所成之導電性樹脂複合材，可獲得表面電阻値爲 • 28 - 201027565 ΙΟ3〜ΙΟ12 Ω /□之良好導電性、成形性相關之破斷延伸之改 善及碳纖維自樹脂複合材之脫落減低之特性。具有表面電 阻値爲1 〇3~ 1 0 12 Ω /□之導電性之該導電性樹脂複合材適用 於例如載帶等1C零件包裝體或磁頭之運送用托盤。爲了 使精密半導體零件免於因靜電而遭破壞，雖於零件容器、 製造場所之地板材等中使用導電性樹脂，但該情況下之該 導電性樹脂之表面電阻値較好爲106〜101 2 Ω /□。該容器之 0 電阻値過低時，累積之靜電急遽朝該容器移動，而產生放 電現象’由此導致該零件短路。相對於此，電子零件容器 之表面電阻値爲1〇6〜1012 Ω /□時，靜電不會引起短路，而 是於該容器側自帶電之電子零件上緩慢地除去。。 又’上述導電性樹脂複合材料可保持優異之導電性之 同時，可獲得30%以上之破斷延伸率，且較好獲得4〇%以 上之破斷延伸，藉此顯示與成形性相關之流動性或耐割裂 性優異之特性。 φ 又，就降低碳纖維自上述導電性樹脂複合材料之脫落 性之方面而Θ，具體而g ’係表不爲將該複合材料（5〇χ9〇 x3mm)浸漬於2〇OOml超純水中，施加47kHz之超音波6〇 秒後，自該複合材料之表面脫落之粒徑0.5μιη以 之數墓爲該複合材之每單fit表面積5000個/ em2以下，較 好爲2500個/cm2以下。 就製造本發明之導電性樹脂複合材料而言，於 _ _ ^ 維添加混合於上述樹脂中，製造導電性樹脂複合材 並沒有特別限制。然而，由於碳纖維之分散上必須有胃 -29- 201027565 之混練性，因此以使用雙軸擠出機熔融混練樹脂與碳纖維 較佳。又本發明之導電性樹脂複合材料由於其特性而具有 可利用熱負荷大之大型雙軸擠出機之優點。 雙軸擠出機之代表例可具體的舉例爲例如ZSK(Werner & Pfleiderer公司製造，商品名）。同樣類型之具體例爲TEX(日 本製鋼所（股）製造，商品名）、TEM(東芝機械（股）製造，商品 名）、KTX(神戶製鋼所（股）製造，商品名）等。另外， FCM(Farrel公司製造，商品名）、Ko-Kneader(Buss公司製 造，商品名）及DSM (Krauss-Maffei公司製造，商品名）等熔 融混練機。上述中更好爲以ZSK爲代表之類型。該ZSK 類型之雙軸擠出機中包含其螺桿爲完全嚙合形、螺桿爲包 含長度與間距不同之各種螺桿區段、以及寬度不同之各種 捏合盤（或相當於其之混練用區段）者。 雙軸擠出機中更好之態樣如下所述。螺桿形狀可使用 1條、2條、或者3條螺紋螺桿，尤其好的是可使用熔融 樹脂之運送能力或剪切混練能力兩者之適用範圍廣的2條 螺紋螺桿。雙軸擠出機之螺桿的長度（L)與直徑（D)之 比（L/D )較好的是20〜50，進而好的是28〜42。L/D較 大者容易實現均質之分散，另一方面，於過大之情形時， 容易由於熱劣化而引起母材樹脂之分解。螺桿上必需具有 1處以上的由用以提高混練性之捏合盤區段（或者與其相 當之混練區段）構成的混練區域，較好的是具有1〜3 處。 作爲擠出機較好使用具有可使原料中之水分或自熔融 -30- 201027565 混練樹脂產生之揮發氣體脫氣之排氣口者。排氣口較好設 置有用以將產生之水分或揮發氣體有效地排出於擠出機外 部之真空泵。又爲了提高碳纖維之分散性，極力去除樹脂 複合材料中之雜質，亦可進行水、有機溶劑、及超臨界流 體等之添加。進而亦可將用以除去擠出原料中所混入之異 物等的篩網設置於擠出機模頭前之區域，以將異物自樹脂 複合材料中去除。作爲該篩網，可列舉金屬絲網、換網 Φ 器、燒結金屬板（圓盤濾片等）等。 將碳纖維供給至擠出機之方法並無特別限制，以下方 法爲代表性之例示。（〇將碳纖維與樹脂獨立供給於擠出機 之方法，（i〇使用超混練機等混合機預混合碳纖維與樹脂 粉末後’供給於擠出機之方法，（m)預先熔融混練碳纖維 與樹脂使其主要顆粒化，將其作爲碳纖維源而供給之方 法。使用纖維外徑分布不同之碳纖維時，可在上述（〇之步 驟前使碳纖維彼此混合，且亦可在上述（i)~(ni)之步驟之 φ 際使碳纖維彼此混合。 以下基於實施例更具體說明本發明，但本發明並不受 該等實施例之任何限制。 [實施例1 ] 碳纖維之調製 使用圖2所示之製造裝置，以下表1所示之條件獲得 稱爲粗徑品（製造例-1)及細徑品（製造例_2)之碳纖維群之 中間體後’在氬氣中900°C下燒成，對作爲雜質所含之焦 -31 - 201027565 油等之烴進行分離及純化。接著使該中間體在氬氣中進行 2 600 °C之高溫熱處理（退火處理），再經氣流粉碎機解碎’ 獲得由碳纖維之三次元網絡構造體構成之碳纖維之集合 am 體。 所得之粗徑品（製造例-1)之碳纖維群之平均纖維外徑 爲117nm，纖維外徑（nm)分布之標準偏差爲26。另一方 面，細徑品（製造例-2)之碳纖維群之平均纖維外徑爲 58nm，纖維外徑（nm)分布之標準偏差爲13。 [表1] 項目 製造例-1 製造例-2 每單位反應爐剖面積之觸媒量(mol/m2/min) 0.14 0.38 每單位反應爐剖面積之烴原料量(mol/m2/min) 13.4 9.4 載氣流量(Nl/min) 1250 1850 原料投入溫度(°C) 400 400 反應爐下部溫度(°C) 900 900 反應爐上部溫度(°c) 1300 1300 所得碳纖維之類型 粗徑品 細徑品 [實施例2] 導電性複合材料之調製 使實施例1獲得之粗徑品與細徑品之碳纖維以5 ·· 1 之質量比在密閉槽中攪拌2小時以上，且混合均質化。將 6.38質量份數之如此獲得之平均纖維直徑102nm之混合物 (圖3)添加於聚碳酸酯樹脂（Lexan141R(商品名，SABIC Inovative Plastics公司製造）中，且均勻混合。使用螺桿 -32- 201027565 直徑30mm之排氣式雙軸押出機TEX-30XSST(商品名，日 本製鋼所（股）製造），將該混合物供料於最後部之第一投入 口中。該擠出機自第一供料口至第二供料口之間設有捏合 盤（Kneading Disk)所成之混練區域，在其正後方設置開放 之排氣口。排氣口之長度相對於螺桿直徑（D)約爲2D。於 該排氣口之後設置側進料器，在側進料器之後進一步設置 有捏合盤之混練區域及與其相連之排氣口。該部分之排氣 φ 口長度約爲1.5D ’使用真空栗使該部份成爲約3kPa之減 壓度。擠出係在料筒溫度300 °C (自螺桿根部之滾筒大致均 等地上升至模頭位置）、螺桿轉數爲1 8 Orpm，及每小時之 吐出量爲20kg條件下進行。將擠出之股線在水浴中冷卻 後，利用造粒機切斷而使其顆粒化。將所獲得之顆粒於 120°C下乾燥5小時，再利用熱風循環式乾燥機於100°C下 乾燥 2 4 小時後，使用射出成形機（東芝機械 IS55FPB)，於料筒溫度爲300°C、模具溫度爲80°C、射 φ 速爲20 mm/sec、以及成形週期約爲60秒之條件下，製作 評價用試驗片。 [比較例1 ] 導電性樹脂複合材料之調製 將6.3 8質量份數之實施例1中獲得之粗徑品碳纖維 添加於上述聚碳酸酯樹脂中’以與實施例2相同之方法製 備評價用試驗片。 -33- 201027565 [比較例2] 導電性樹脂複合材料之調製 將7.53質量份數之實施例1中獲得之粗徑品碳纖維 添加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製 備評價用試驗片。 [比較例3 ] 導電性樹脂複合材料之調製 @ 將4.17質量份數之實施例1中獲得之細徑品碳纖維 添加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製 備評價用試驗片。 [比較例4 ] 導電性樹脂複合材料之調製 將6.3 8質量份數之實施例1中獲得之細徑品碳纖維 添加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製 Q 備評價用試驗片。 [實施例3] 導電性樹脂複合材料之調製 使實施例1中獲得之細徑品與粗徑品之碳纖維以2 : 3 之質量比在密閉槽中攪拌2小時以上’混合均質化後’以 5.0質量份數添加於上述聚碳酸酯樹脂中’以與實施例2 相同之方法製備評價用試驗片。 -34- 201027565 [實施例4] 導電性樹脂複合材料之調製 使實施例1中獲得之細徑品與粗徑品之碳纖維以1 : 2 之質量比在密閉槽中攪拌2小時以上，混合均質化後，以 6.0質量份數添加於上述聚碳酸酯樹脂中，以與實施例2 相同之方法製備評價用試驗片。 [實施例5] 導電性樹脂複合材料之調製 使實施例1中獲得之細徑品與粗徑品之碳纖維以3 : 5 之質量比在密閉槽中攪拌2小時以上，混合均質化後，以 8.0質量份數添加於上述聚碳酸酯樹脂中，以與實施例2 相同之方法製備評價用試驗片。Further, the above-mentioned three-dimensional network-like carbon fiber structure is such that the carbon fibers existing in the three-dimensional network form are bonded to each other during the growth process, and it is preferable that the carbon fiber structure has a plurality of spaces in the three-dimensional space as described above. The carbon fibers present in the three-dimensional space are bonded to each other on the formed granular portion during the growth process, and therefore, the electrical properties of the structure itself are excellent, for example, at a certain compression density. The powder resistance 测定 measured at 88g/cm3 is 〇〇25ω·cm or less, more preferably 〇·〇〇5~0.020Ω·cm. If the powder resistance 値 exceeds 0.025 Ω · cm, it is difficult to produce a good conductive -18- 201027565 composite material when it is composited with a resin. Further, since the above-described three-dimensional network-like carbon fiber structure has high strength and electrical conductivity, it is preferable to form a carbon fiber. The graphene sheet has less defects, specifically, for example, ID/IG measured by Rayman spectrometry. It is better than 0.2 or less 'better than 0.1 or less. Among them, the large single crystal graphite in the Lehman spectroscopic analysis only showed a peak near the peak of i 5 80 cm·1 (G band). The φ peak (D band) near 1 3 6 OcnT 1 appears due to the finite crystal size or lattice defect of the crystal. Therefore, the intensity ratio of the D band to the G band (R = I136g / I158G = Id / IG) is considered to be less than the specific enthalpy as described above, and the amount of defects in the graphene sheet is small. The term "defect" as used herein refers to an incomplete arrangement of graphene sheets due to intrusion of unnecessary atoms as impurities in the arrangement of graphene sheets constituting the intermediate, or insufficient carbon atoms or offset. Part (lattice defect) and the like. Further, although not particularly limited, the combustion starting temperature of the carbon φ fibers in the three-dimensional network form in air is preferably 700 ° C or higher, more preferably 750 to 900 ° C. The above-mentioned three-dimensional network-like carbon fiber has such a high heat stability because it has few defects and the carbon fiber has a desired outer diameter. The carbon fiber aggregate of the present invention preferably has a specific surface area of 10 to 60 m 2 /g. When the specific surface area is as large as 60 m 2 /g or more, the outer diameter of the carbon fiber becomes fine, and it becomes difficult to disperse or the like. On the other hand, when the specific surface area is 1 〇m2/g or less, the number of carbon fibers per unit amount is extremely small, so that it is difficult to obtain a composite material having high conductivity when added in a small amount. -19- 201027565 The carbon fiber structure having the above characteristics is not particularly limited', but can be prepared, for example, as follows. Basically, an organic compound such as a hydrocarbon is thermally decomposed by a CVD method using a transition metal ultrafine particle as a catalyst to obtain a fiber structure (hereinafter referred to as an intermediate body), which is further subjected to high-temperature heat treatment. As the raw material organic compound, a hydrocarbon such as benzene, toluene or xylene, an alcohol such as carbon monoxide (CO) or ethanol, or the like can be used. Although it is not particularly limited, it is preferred to use at least two or more carbon compounds having different decomposition temperatures as the carbon source for obtaining the fiber structure of the present invention. In addition, the term "at least two or more kinds of carbon compounds" as used in the present specification is not necessarily a raw material organic compound which is required to use two or more types, and also includes a fiber structure in the case of using one organic compound as a raw material. During the synthesis reaction, for example, a reaction such as hydrodealkylation of toluene or xylene may occur, and in the subsequent thermal decomposition reaction system, it is a state in which two or more carbon compounds having different decomposition temperatures are formed. Further, when two or more kinds of carbon compounds are present as a carbon source in the thermal decomposition reaction system, the decomposition temperature of each carbon compound varies not only with the kind of the carbon compound but also with the gas partial pressure of each carbon compound in the raw material gas and Mohr. The ratio varies, and therefore, by adjusting the composition ratio of two or more kinds of carbon compounds in the material gas, a relatively large combination can be used as the carbon compound. For example, it is derived from alkane such as methane, ethane, propane such as 'butanes, pentanes, hexanes, heptanes, cyclopropanes, cyclohexanes, and naphthenes, especially about 1 to 7 carbon atoms. Alkenes; ethylene, propylene, butenes, pentenes, heptenes, cyclopentenes and other alkenes and cycloolefins, especially carbon number 1~7-20-201027565 olefins; acetylene, propylene Alkynes such as alkyne, especially carbon 1 to 7 benzene, toluene, styrene, xylene, naphthalene, methylnaphthalene' and heteroaromatic hydrocarbons, especially aromatic hydrocarbons having a carbon number of 6 to 18; methanol, Alcohols such as ethanol, especially carbons; other compounds selected from the group consisting of carbon oxides, ketones, ethers, etc., can be adjusted in such a manner as to be in the desired thermal decomposition reaction temperature range, and the gas partial pressure, combined use, and/or φ The residence time is adjusted in the degree region, and the fiber assembly (intermediate) is produced by optimizing the mixing ratio. In the combination of these two or more kinds of carbon compounds, for example, it is preferable that the mixture is in the range of from 1 to 600%, preferably from 3 to 100. Further, when the enthalpy is the reactor inlet ratio, for example, when toluene is used as one of the carbon sources, it is considered that 100% of toluene is decomposed and methane and benzene are produced at 1:1, and it may be supplied by other means. For example, methane/benzene ΐ Φ is relative to 1 mole of toluene, and 2 moles of methane is added to the toluene. For the added methane, the method of not using fresh methane can also be used to recycle Unreacted methane contained in the discharged exhaust gas. By setting the composition ratio within this range, a three-dimensional network structure (intermediate) in which either of the specific portion and the granular portion is highly developed can be obtained. In addition, it is not necessarily limited, but the factors for controlling the fibers are as follows: acetylenes of the right and left; aromatic aromatics such as ruthenium and phenanthrene; and alcohols of two or more kinds of alcohols having a heteroaryl group of about 1 to 7 can be decomposed at a specific temperature. The methane and benzene groups can be efficiently used, 1.1 to 200, and the gas composition is more than 3 in the reaction furnace. Furthermore, if only the outer diameter of the outer diameter of the fiber having a fine carbon fiber structure from the reaction furnace is utilized, 21 - 201027565 1) the concentration of the hydrocarbon compound in the raw material 2) the concentration ratio of the hydrocarbon compound to the catalytic metal in the raw material 3 ) The residence time in the reactor. In order to make the outer diameter of the carbon fiber coarse, it is only necessary to increase the concentration of the hydrocarbon compound in the raw material. Further, in the ratio of the concentration of the hydrocarbon compound to the catalytic metal in the raw material, in order to make the outer diameter somewhat coarse, the molar ratio of the hydrocarbon compound to the catalytic metal is such that the molar ratio of the catalytic metal is only slightly higher. can. In the chemical vapor phase growth method (CVD method), a catalytic metal is used as a core, and it is also preferable to increase the amount of the metal catalyst to further grow the carbon fiber. Further, an inert gas such as argon gas, helium gas or neon gas or hydrogen may be used as the atmosphere gas. Further, as the catalyst, a transition metal such as iron, cobalt or molybdenum or a mixture of a transition metal compound such as ferrocene or a metal acetate or a sulfur compound such as sulfur or thiophene or iron sulfide is used. As the synthesis of the intermediate, a CVD method such as a hydrocarbon which is usually carried out can be used. The mixture of the smoke and the catalyst which is a specific raw material is evaporated, and chlorine or the like is introduced into the reaction furnace as a carrier gas, and is thermally decomposed at a temperature of 800 to 1300 °C. By combining a plurality of carbon fiber structures (intermediates) into a collection of several centimeters to tens of centimeters in size, the carbon fiber structure having fibers having an outer diameter of 100 to 300 nm by mutual contact A loose three-dimensional structure in which a particle of a medium grows as a nucleus and is a granular body. The manufacturing apparatus including the above reaction furnace is not particularly limited, but a manufacturing apparatus having a configuration such as that shown in Fig. 2 can be exemplified. In the manufacturing apparatus -22-201027565 shown in the drawing, the raw material is evaporated, the vaporized raw material is mixed with the carrier gas, and the raw material mixed gas is introduced into the inside of the reaction furnace 8, and the carbon fiber manufacturing apparatus is manufactured in the reaction furnace 8. 1 is provided with a raw material tank 2 containing a raw material, and a gas tank 4 for transporting a raw material and a carrier gas introduced into the reaction furnace 8, and the raw material tank 2 and the gas tank 4 are respectively passed through the raw material introduction pipe 3 and the gas introduction pipe 5 Connected to the evaporator 6. Further, the evaporator 6 is connected to the reaction furnace 8 through the raw material mixed gas introduction pipe 7. In addition, the reaction furnace 8 φ in which the carbon fiber is produced is formed into a cylindrical shape, and the introduction nozzle 9 for introducing the mixed raw material gas into the inside of the reaction furnace 8 is provided at one end of the axial direction. Further, the inside of the reaction furnace 8 is provided with a heater as a heating means 11 to heat the inside of the reaction furnace 8 from the outer periphery of the reaction furnace 8. Next, a carbon fiber collector 12 for storing and recovering the produced carbon fibers is connected to the lower end side of the other end of the reaction furnace 8 in the axial direction. A gas discharge pipe 13 for exhausting gas is connected to the carbon fiber recovery unit 12. The thermal decomposition reaction of the hydrocarbon to be a raw material occurs mainly on the surface of the granular material in which the catalyst particles or φ grows as the core of the catalyst particles, and the recrystallization of carbon due to decomposition proceeds from the catalyst particles to the catalyst particles. The granules are formed in a certain direction and grow into a fibrous shape. However, in order to obtain a carbon network structure having a preferred three-dimensional network shape of the above-described carbon fiber, the balance between the thermal decomposition rate and the growth rate is intentionally changed, for example, at least two or more kinds of carbons having different decomposition temperatures as described above are used. The compound acts as a carbon source, so that the carbon material grows not only in the primary direction, but also the carbon material grows toward the third element centering on the granular body. However, the growth of these three-dimensional carbon fibers does not depend solely on the equilibrium between the thermal decomposition rate and the growth rate, but also on the crystal surface of the catalyst particles -23- 201027565, the residence time in the reactor, the temperature distribution in the furnace, etc. In addition, the balance between the thermal decomposition reaction and the growth rate is affected not only by the type of the carbon source as described above, but also by the reaction temperature and the gas temperature, but in other words, if the growth rate is higher than the thermal decomposition rate described above, When the carbon material grows rapidly, the carbon material grows into a fibrous shape. On the other hand, if the rate of thermal decomposition is faster than the growth rate, the carbon material grows in the circumferential direction of the catalyst particles. Therefore, by deliberately changing the balance between the thermal decomposition rate and the growth rate, the three-dimensional structure of the present invention can be formed in a plurality of directions under the control, as long as the growth direction of the carbon material does not become a constant direction. Further, in the intermediate formed, the three-dimensional structure as described above is easily formed by bonding the fibers to the granules, and the composition of the catalyst or the like, the residence time in the reaction furnace, the reaction temperature, and The gas temperature and the like are optimized. In addition, as a method of efficiently producing a fiber structure (intermediate), in addition to a method of using two or more kinds of carbon compounds having different decomposition temperatures as described above as an optimum mixing ratio, it may be supplied The raw material gas of the reactor generates a turbulent flow in the vicinity of the supply port. The term "turbulent flow" as used herein refers to a highly turbulent air flow, and refers to a flow of a swirling flow. In the reactor, the raw material gas is introduced into the reaction furnace from the supply port, and immediately after the decomposition of the transition metal compound as a catalyst in the raw material mixed gas, the metal catalyst fine particles are formed, but they also undergo the following stages. That is, first, the transition metal compound is decomposed into metal atoms, and then, cluster formation is caused by a plurality of collisions of metal atoms of, for example, about 100 atoms. At the stage of the formation of the cluster, it does not function as a catalyst for the fiber structure (intermediate), and further merges into a crystal of about 3 nm to ΙΟηιη by the collision of the generated clusters -24-201027565. The "particles" are used as metal catalyst particles for the production of carbon fiber structures (intermediates). During the formation of the catalyst, if there is eddy current caused by the intense turbulence as described above, it is possible to perform a more intense collision with the collision of metal atoms or clusters which only perform Brownian motion, thereby When the number of collisions per unit time is increased, the metal catalyst micro-particles are obtained in a high yield in a short period of time, and the concentration, temperature, and the like are uniformized by eddy currents, whereby metal catalyst particles having the same particle size can be obtained. Further, in the process of forming the metal catalyst fine particles, an aggregate of metal catalyst fine particles in which a large amount of crystalline crystal particles are aggregated is formed by the intense collision caused by the eddy current. In this manner, the metal catalyst fine particles are rapidly formed, and the area of the surface of the metal catalyst at the decomposition reaction site of the carbon compound is increased. Therefore, the decomposition of the carbon compound is promoted, and the carbon material is sufficiently supplied, and the metal catalyst particles of the aggregate are used as the metal catalyst particles. The nucleus causes the carbon fibers to grow radially. On the other hand, if the thermal decomposition rate of a part of the carbon compounds is faster than the growth rate of the carbon materials as described above, the carbon substances also grow in the circumferential direction of the catalytic particles. A granular portion is formed around the aggregate, and a fiber structure (intermediate) having a desired three-dimensional structure is efficiently formed. Furthermore, it is generally considered that the aggregate of the metal catalyst microparticles also includes a part of the catalyst microparticles having lower activity than other catalyst microparticles or being inactivated during the reaction, and is generally considered to be in the above-mentioned touch before being aggregated into an aggregate. The surface of the granule is grown, or after the formation of the aggregate, the non-fibrous or extremely short fibrous carbon material is grown by using the above-mentioned catalyst microparticles as a nucleus, and is formed by being present at the circumference of the aggregate -25 - 201027565 The granular part of the precursor. Therefore, the granule portion is composed of a plurality of end portions of the vapor-phase carbon fibers and metal catalyst particles for growing the carbon material only in the circumferential direction, and a plurality of granular portions in which the gas phase carbon fibers are bonded to each other are formed in plural. The collection of the spherical structures and the accumulation of the spheres, rather than the simple spheres, because the carbonaceous material continues to grow in this state, and therefore interacts with the annealing treatment described later, and a plurality of gases are collected and accumulated in the granular portion. The end portion of the carbon fiber or the plurality of spherical structures are formed adjacent to each other to form a continuous graphene sheet-like layer, and as a result, a three-dimensional network-like vapor phase carbon fiber structure in which a plurality of gas phase carbon fibers are firmly bonded to each other by a granular portion is formed. body. The temperature of the raw material gas to be supplied in the vicinity of the raw material gas supply port of the reaction furnace is preferably from 3,500 to 450 °C. The specific means for generating a turbulent flow of the raw material gas is not particularly limited, and for example, a method of introducing a raw material gas into a reaction furnace by a swirling flow or a raw material gas which can be caused to interfere with a raw material gas from a raw material gas supply port to the reaction furnace can be employed. A method of setting a certain collision portion or the like at the position of the air current. The shape of the collision portion is not limited, and any turbulent flow in the reaction furnace may be formed by eddy current generated from the collision portion as a starting point. For example, a separator or a paddle of various shapes may be used. The tapered tube, the umbrella body, and the like are arranged in a single or plural form, and are arranged in one or a plurality of forms. In the manufacturing apparatus 1 exemplified in Fig. 2, an example is provided in which the rectifying/buffering plate 10 is provided around the introduction nozzle 9. The rectifying/buffering plate is an obstacle disposed in the vicinity of the introduction nozzle 9 to prevent the flow of the raw material mixed gas from becoming a collision starting point, and the vortex is generated by the collision of the obstacle with the raw material mixed gas to make the temperature distribution and the concentration distribution uniform. It becomes possible. Rectification and conflict -26 - 201027565 There is no restriction on the shape of the plate. The eddy current generated by using the rectifying and buffering plate as a starting point is not destroyed and is successively formed into the shape of the lower end side of the reaction furnace 8. The mixture of the catalyst and the hydrocarbon is set to be 800 to 13 00. (An intermediate obtained by heating under a temperature at a range, having an incomplete structure in which a chip-like sheet made of carbon atoms is attached. If the intermediate is subjected to Lehman spectroscopic analysis, the D band is very large, that is, a defect Further, the produced intermediate contains unreacted raw materials, non-fibrous carbides, tar components, and catalytic metals. Therefore, in order to remove such residues from such intermediates, it is necessary to obtain fewer defects. The carbon fiber structure is heat-treated at a high temperature of 2400 to 3000 t: by an appropriate method. That is, for example, the intermediate is heated at 800 to 1 200 ° C to remove volatile components such as unreacted raw materials or tar components, and then at 2400. ~3000. (: The high temperature is annealed to prepare the desired structure, and at the same time, the catalyst metal contained in the fiber is evaporated and removed. At this time, φ reducing gas or trace amount may be added in an inert gas atmosphere. The carbon monoxide gas is structured as a protective material. If the intermediate is annealed at a temperature in the range of 2400 to 300 CTC, the chip-like flakes formed of carbon atoms can be combined to form a plurality of The graphene sheet-like layer is used to obtain a desired carbon fiber. On the other hand, the resin which can be used in the production of the conductive resin composite material of the present invention is not particularly limited, and examples thereof include, for example, epoxy resin, eucalyptus, and poly Curing resin such as urethane carboxylic acid resin, melamine resin, urea resin, aniline resin, furan resin, alkyd resin, xylene resin, unsaturated polyester resin, diarylate resin, polyparaphenylene Formic acid -27- 201027565 Butadiene ester resin, polyethylene terephthalate resin, polycarbonate, polyoxybenzene, polyphenyl ether, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, Polypropylene, polybutadiene, polyacrylonitrile, polystyrene, polymethyl methacrylate, polyethylene oxide, polybutylene oxide, thermoplastic polyurethane, phenoxy resin, polyfluorene Amine, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/ethyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/ Vinyl acetate/methyl Glycidyl acrylate copolymer, ethylene/propylene-g-maleic anhydride copolymer, polyester polyether elastomer, polytetrafluoroethylene, cellulose acetate, ethyl cellulose, polydimethyl siloxane, Polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl pyrrolidine, sucrose octaacetate, polystyrene, acrylonitrile/butadiene/styrene resin, polychlorinated Ethylene, acrylonitrile/styrene resin, methacrylic resin, vinyl chloride, polyamine, polyacetal' modified polyphenyl ether, polybutylene terephthalate, polyterephthalic acid Ethylene diester, ultra high molecular weight polyethylene, polyphenyl sulfide, polyimide, polyether phthalimide, polyacrylic acid ester, poly milling, polyether oxime, polyether ether ketone, liquid crystal polymer, polytetra A thermoplastic resin such as vinyl fluoride or the like. These resins may be a homopolymer or a copolymer, or a mixture of two or more. The above carbon fibers are added and mixed in the above resin to form a conductive resin composite material of the present invention. The amount of the carbon fibers in the conductive resin composite material is preferably from 1 to 1 to 2 parts by mass, more preferably from 3 to 7.7 parts by mass, based on 1 part by mass of the resin. By adding a conductive resin composite obtained by mixing the required amount of carbon fibers, it is possible to obtain a good surface resistance •28 - 201027565 ΙΟ3~ΙΟ12 Ω /□, good electrical conductivity, improvement in fracture resistance associated with formability, and carbon fiber self-conditioning. The property of the resin composite to reduce the shedding. The conductive resin composite material having a surface resistance 値 of 1 〇 3 to 10 12 Ω / □ is suitable for use in, for example, a 1C component package such as a carrier tape or a transport tray for a magnetic head. In order to prevent the precision semiconductor component from being damaged by static electricity, the conductive resin is used in the component container or the floor material of the manufacturing site, but the surface resistance of the conductive resin in this case is preferably 106 to 101 2 Ω / □. When the 0 resistance of the container is too low, the accumulated static electricity rapidly moves toward the container, causing a discharge phenomenon, thereby causing the part to be short-circuited. On the other hand, when the surface resistance 値 of the electronic component container is 1 〇 6 to 1012 Ω / □, static electricity does not cause a short circuit, but is slowly removed from the charged electronic component on the container side. . Further, the above-mentioned conductive resin composite material can maintain excellent electrical conductivity and obtain a breaking elongation of 30% or more, and preferably obtain a breaking elongation of 4% by or more, thereby showing a flow associated with formability. Excellent or resistant to splitting. φ Further, in order to reduce the detachment of the carbon fiber from the above-mentioned conductive resin composite material, specifically, the composite material (5〇χ9〇x3 mm) is not immersed in 2 OOml of ultrapure water. After the ultrasonic wave of 47 kHz is applied for 6 sec seconds, the particle diameter of 0.5 μm from the surface of the composite material is 5,000 pieces per em surface area per em fit, preferably 2,500 pieces/cm 2 or less. The conductive resin composite material of the present invention is not particularly limited as long as it is added to the above resin in the _ _ ^ dimension to produce a conductive resin composite. However, since the dispersion of the carbon fibers must have the kneading property of the stomach -29-201027565, it is preferable to melt-knead the resin and the carbon fibers by using a twin-screw extruder. Further, the conductive resin composite material of the present invention has the advantage of being able to utilize a large-sized twin-screw extruder having a large heat load due to its characteristics. A representative example of the twin-screw extruder can be specifically exemplified by, for example, ZSK (manufactured by Werner & Pfleiderer, trade name). Specific examples of the same type are TEX (manufactured by Japan Steel Works Co., Ltd., trade name), TEM (manufactured by Toshiba Machine Co., Ltd., trade name), KTX (manufactured by Kobe Steel Works Co., Ltd., trade name), and the like. Further, FCM (manufactured by Farrel Co., Ltd., trade name), Ko-Kneader (manufactured by Buss Co., Ltd., trade name), and DSM (manufactured by Krauss-Maffei Co., Ltd., trade name) melt kneading machine. The above is preferably a type represented by ZSK. The ZSK type twin-screw extruder includes a screw having a fully meshed shape, and the screw is composed of various screw segments having different lengths and pitches, and various kneading discs having different widths (or a kneading section corresponding thereto). . A better aspect of the twin screw extruder is as follows. The screw shape may be one, two, or three threaded screws, and it is particularly preferable to use two threaded screws having a wide range of application of the molten resin or the shearing kneading ability. The ratio (L/D) of the length (L) to the diameter (D) of the screw of the twin-screw extruder is preferably 20 to 50, and more preferably 28 to 42. The larger the L/D is, the easier it is to achieve homogenous dispersion. On the other hand, when it is too large, it is liable to cause decomposition of the base resin due to thermal deterioration. It is necessary to have one or more kneading regions composed of kneading disc segments (or a kneading section thereof) for improving kneading on the screw, and it is preferable to have 1 to 3 portions. As the extruder, it is preferred to use an exhaust port which can deaerate the moisture in the raw material or the volatile gas generated from the molten -30-201027565 kneading resin. The exhaust port is preferably provided with a vacuum pump for efficiently discharging the generated moisture or volatile gas to the outside of the extruder. In order to improve the dispersibility of the carbon fibers, the impurities in the resin composite material are removed as much as possible, and water, an organic solvent, and a supercritical fluid may be added. Further, a screen for removing foreign matter or the like mixed in the extruded raw material may be placed in a region in front of the extruder die to remove foreign matter from the resin composite material. Examples of the screen include a wire mesh, a mesh changing device, a sintered metal plate (such as a disk filter), and the like. The method of supplying the carbon fibers to the extruder is not particularly limited, and the following methods are representative examples. (〇 A method in which carbon fiber and resin are independently supplied to an extruder, (i) a method of supplying carbon fiber and resin powder by a mixer such as an ultra-kneader, and then supplying it to an extruder, (m) pre-melting and kneading carbon fiber and resin A method in which it is mainly granulated and supplied as a carbon fiber source. When carbon fibers having different fiber outer diameter distributions are used, the carbon fibers may be mixed with each other before the step (〇), and may also be in the above (i) to (ni) The carbon fiber is mixed with each other in the step φ. The present invention will be more specifically described below based on the examples, but the present invention is not limited by the examples. [Example 1] Modification of carbon fiber is carried out using the production shown in Fig. 2 The apparatus was obtained by the conditions shown in Table 1 below, and the intermediates of the carbon fiber group called the large diameter product (Production Example-1) and the small diameter product (Production Example 2) were fired at 900 ° C in argon gas. The hydrocarbons such as coke-31 - 201027565 oil contained in the impurities are separated and purified, and then the intermediate is subjected to high-temperature heat treatment (annealing treatment) at 2 600 ° C in argon gas, and then decomposed by a jet mill. Obtained by carbon The aggregate of the carbon fibers composed of the three-dimensional network structure of the dimension is obtained. The average fiber outer diameter of the carbon fiber group of the obtained large diameter product (Production Example-1) is 117 nm, and the standard deviation of the fiber outer diameter (nm) distribution is 26. On the other hand, the average fiber outer diameter of the carbon fiber group of the small diameter product (Production Example-2) was 58 nm, and the standard deviation of the fiber outer diameter (nm) distribution was 13. [Table 1] Item Manufacturing Example-1 Manufacturing Example-2 The amount of catalyst per unit area of the reactor (mol/m2/min) 0.14 0.38 The amount of hydrocarbon feed per unit of reactor cross section (mol/m2/min) 13.4 9.4 Carrier gas flow rate (Nl/min) 1250 1850 Raw material input Temperature (°C) 400 400 Temperature of the lower part of the reactor (°C) 900 900 Temperature of the upper part of the reactor (°c) 1300 1300 Type of carbon fiber obtained Large diameter diameter product [Example 2] Modification of conductive composite material The carbon fiber obtained in Example 1 and the carbon fiber of the small diameter product were stirred in a closed tank for 2 hours or more at a mass ratio of 5 ··1, and homogenized by mixing. 6.38 parts by mass of the mixture of the average fiber diameter of 102 nm thus obtained was obtained. (Fig. 3) added to polycarbonate resin (Lexan141R (trade name, SAB) Manufactured by IC Inovative Plastics Co., Ltd., and uniformly mixed. The screw was supplied to the TEX-30XSST (trade name, manufactured by Nippon Steel Works Co., Ltd.) with a screw-32-201027565 30 mm diameter exhaust type. In the first input port of the last part, the extruder is provided with a kneading disk formed by a Kneading Disk from the first supply port to the second supply port, and an open exhaust port is arranged directly behind the Kneading Disk. . The length of the vent is about 2D with respect to the screw diameter (D). A side feeder is disposed after the exhaust port, and a kneading zone of the kneading disc and an exhaust port connected thereto are further disposed after the side feeder. The portion of the exhaust gas φ port has a length of about 1.5 D. The vacuum pump is used to make the portion a depressurization of about 3 kPa. The extrusion was carried out at a cylinder temperature of 300 ° C (the drum from the root of the screw was substantially uniformly raised to the position of the die), the number of revolutions of the screw was 18 rpm, and the discharge amount per hour was 20 kg. After the extruded strands were cooled in a water bath, they were cut by a granulator to be pelletized. The obtained granules were dried at 120 ° C for 5 hours, and then dried at 100 ° C for 24 hours using a hot air circulating dryer, and then an injection molding machine (Toshiba Machine IS55FPB) was used at a cylinder temperature of 300 ° C. A test piece for evaluation was produced under the conditions of a mold temperature of 80 ° C, a shot φ speed of 20 mm/sec, and a molding cycle of about 60 seconds. [Comparative Example 1] Preparation of Conductive Resin Composite Material A test for evaluation was prepared in the same manner as in Example 2 by adding 6.3 parts by mass of the large diameter carbon fiber obtained in Example 1 to the above polycarbonate resin. sheet. -33-201027565 [Comparative Example 2] Preparation of Conductive Resin Composite Material 7.3 parts by mass of the large diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin, and the same procedure as in Example 2 was carried out. Test piece for evaluation. [Comparative Example 3] Preparation of Conductive Resin Composite Material @ 4.17 parts by mass of the fine-diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin, and an evaluation test was prepared in the same manner as in Example 2. sheet. [Comparative Example 4] Preparation of Conductive Resin Composite Material 6.3 8 parts by mass of the fine-diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin, and the same procedure as in Example 2 was carried out. Use test strips. [Example 3] Preparation of conductive resin composite material The carbon fiber of the small diameter product and the large diameter product obtained in Example 1 was stirred in a closed tank for 2 hours or more at a mass ratio of 2:3, after mixing and homogenization. 5.0 parts by mass was added to the above polycarbonate resin. A test piece for evaluation was prepared in the same manner as in Example 2. -34-201027565 [Example 4] Preparation of conductive resin composite material The carbon fiber of the small diameter product and the large diameter product obtained in Example 1 was stirred in a sealed tank for 2 hours or more at a mass ratio of 1:2, and the mixture was homogenized. After the addition, the test piece for evaluation was prepared in the same manner as in Example 2, by adding it to the above polycarbonate resin in an amount of 6.0 parts by mass. [Example 5] Preparation of conductive resin composite material The carbon fiber of the small diameter product and the large diameter product obtained in Example 1 was stirred in a sealed tank for 2 hours or more at a mass ratio of 3:5, and after homogenization, 8.0 parts by mass was added to the above polycarbonate resin, and a test piece for evaluation was prepared in the same manner as in Example 2.
[比較例5 ] 導電性樹脂複合材料之調製 將4.0質量份數之實施例1中獲得之細徑品碳纖維添 加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製備 評價用試驗片。 [比較例6 ] 導電性樹脂複合材料之調製 將5.0質量份數之實施例1中獲得之細徑品碳纖維添 -35- 201027565 加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製備 評價用試驗片。 [比較例7] 導電性樹脂複合材料之調製 將6.0質量份數之實施例1中獲得之粗徑品碳纖維添 加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製備 評價用試驗片。 [比較例8 ] 導電性樹脂複合材料之調製 將7.0質量份數之實施例丨中獲得之粗徑品碳纖維添 加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製備 評價用試驗片。 [比較例9 ] 導電性樹脂複合材料之調製 將8.0質量份數之實施例1中獲得之粗徑品碳纖維添 加於上述聚碳酸酯樹脂中，以與實施例2相同之方法製備 評價用試驗片。 導電性樹脂複合材料之物性係依循下列方法測定。 (1)表面電阻 參照JIS K 7194(以導電性塑膠之四探針法進行之電 201027565 阻試驗方法），測定位置及測定方法係以其爲準，使用 Loresta GP (MCP-T60型，三菱化學（股）製造，商品名）、 Hiresta UP(MCP-HT450型，三菱化學（股）製造，商品 名），測定射出成形之試驗片（5 0x90x3 mm)之表面電阻。所 得結果示於表2及表3中。 (2)體積電阻 _ 自射出成形試驗片切割出20mmx20mmx厚度2.5mm之 響 試料片，在20mmx2.5mm之二平行側面上塗佈銀膠（德力 化學股份有限公司製造，Silvest P-248)，並黏著約l〇cm 之銅線電極之端部。使該銅線電極以耐壓夾及專用電纜連 接於直流電壓•電源/Monita R6243(ADC股份有限公司製 造）之輸出入端子。使用該裝置，藉由二端子法測定試料 之體積電阻Rv(單位爲Qcm)。施加電壓V(單位V)，記錄 讀取之電流値（I :單位爲A)。試料之體積電阻Rv係由電 φ 流方向之剖面積S =試料寬度Wx厚度t(單位爲cm2)及試料 長度L(單位爲cm) ’使用試料電阻之測定値R = (V/I),可 計算出體積電阻Rv = (V/I)xWxt/L(ncm)。上述試料成爲 W = 2cm ’ L = 2cm ’ t = 0.2 5cm。所得體積電阻結果列於表3。 (2)破斷延伸率 以IS0527-1(通則）及527-2(模型成型、擠出成型及注 模塑膠之試驗條件）爲準測定拉伸破斷延伸率。射出成形 之試驗片之形狀及尺寸爲IS〇527-2之試驗片1A形。試驗 -37- 201027565[Comparative Example 5] Preparation of conductive resin composite material 4.0 parts by mass of the fine-diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin, and a test piece for evaluation was prepared in the same manner as in Example 2. . [Comparative Example 6] Preparation of Conductive Resin Composite Material 5.0 parts by mass of the fine-diameter carbon fiber addition-35-201027565 obtained in Example 1 was added to the above polycarbonate resin in the same manner as in Example 2. A test piece for evaluation was prepared. [Comparative Example 7] Preparation of Conductive Resin Composite Material A test piece for evaluation was prepared in the same manner as in Example 2, except that 6.0 parts by mass of the large diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin. . [Comparative Example 8] Preparation of conductive resin composite material 7.0 parts by mass of the large diameter carbon fiber obtained in Example 添加 was added to the above polycarbonate resin, and a test piece for evaluation was prepared in the same manner as in Example 2. . [Comparative Example 9] Preparation of conductive resin composite material 8.0 parts by mass of the large diameter carbon fiber obtained in Example 1 was added to the above polycarbonate resin, and a test piece for evaluation was prepared in the same manner as in Example 2. . The physical properties of the conductive resin composite material were measured in accordance with the following methods. (1) Surface resistance refers to JIS K 7194 (Electrical 201027565 resistance test method using four-probe method of conductive plastic), and the measurement position and measurement method are based on it, using Loresta GP (MCP-T60 type, Mitsubishi Chemical) (manufactured by the company), Hiresta UP (Model MCP-HT450, manufactured by Mitsubishi Chemical Corporation, trade name), and the surface resistance of the test piece (50x90x3 mm) for injection molding was measured. The results obtained are shown in Tables 2 and 3. (2) Volume resistance _ The test piece of 20 mm x 20 mm x thickness of 2.5 mm was cut out from the injection-molded test piece, and silver glue (Silvest P-248, manufactured by Deli Chemical Co., Ltd.) was coated on the parallel side of 20 mm x 2.5 mm. And adhere to the end of the copper wire electrode of about l〇cm. The copper wire electrode was connected to a DC voltage source/power supply/Monita R6243 (manufactured by ADC Co., Ltd.) output terminal with a voltage clamp and a dedicated cable. Using this apparatus, the volume resistance Rv (unit: Qcm) of the sample was measured by a two-terminal method. Apply a voltage V (unit V) and record the read current 値 (I: unit is A). The volume resistance Rv of the sample is the cross-sectional area of the electric φ flow direction S = sample width Wx thickness t (unit: cm2) and the sample length L (unit: cm) 'measurement of the sample resistance 値R = (V/I), The volume resistance Rv = (V/I) x Wxt / L (ncm) can be calculated. The above sample became W = 2 cm ′ L = 2 cm ′ t = 0.2 5 cm. The resulting volume resistance results are shown in Table 3. (2) Breaking elongation The tensile elongation at break was measured in accordance with IS0527-1 (General Rules) and 527-2 (Test Conditions for Modeling, Extrusion, and Injection Molding). The test piece of the injection molding was in the shape of a test piece 1A of IS 〇 527-2. Test -37- 201027565
裝置係使用萬能材料試驗機（Intesco 2005-5型），試驗速 度爲 50mm/min，夾具間距離爲115mm，在23°C 50%RH 之試驗環境下進行。與上述同樣成型並算出所測定之5片 試驗片之破斷延伸率値之平均値。所得結果列於表2。 (3)脫落性 將2000毫升超純水注入經超純水洗淨之3000毫升玻璃 燒杯中，且浸漬一片射出成形之試驗片（50x90x3mm)。隨後， 以 5210E-DTH(47kHz/140W)(商品名，BRANSON 公司製造）施 加超音波1分鐘。隨後，以液中微粒子計測器HIAC ROYCO SYSTEM801 1 (商品名，HACH ULTRA AN ALYTIC S 公司製 造）吸引該抽出之超純水，測定塵埃粒子直徑0.5 μιη以上 之發塵量。所得結果列於表2。 [表2] 實施例2 比較例1 比較例2 比較例3 比較例4 微細碳纖維 類型 混合品 粗徑品 粗徑品 細徑品 細徑品 平均纖維直徑(nm) 102 117 117 58 58 纖維徑標準偏差 36 26 26 13 13 質量份 6.38 6.38 7.53 4.17 6.38 聚碳酸酯 質量份 100 100 100 100 100 表面電阻 Ω/cm2 2.75χ1〇5 6.33X106 1.38x10s 5.08x105 5.23x103 破斷延伸率 % 60 40 32 27.1 22 脫落性 - 〇 〇 〇 〇 〇 ※混合品...細徑品：粗徑品=1 : 5(質量比） ※脫落性…〇.5μηι以上之發塵量以5,000個/cm2作爲基準値 (規格値），在其以下者判定爲〇。 201027565 [表3] 實施例3 實施例4 實施例5 比較例5 比較例ό 比較例7 比較例8 比較例9 微細碳 纖維 類型 混合品 混合品 混合品 細徑品 細徑品 粗徑品 粗徑品 粗徑品 細徑品: 粗徑品 2:3 (質量比) 1:2 (質量比) 3:5 (質量比) 僅細徑品 僅細徑品 僅粗徑品 僅粗徑品 僅粗徑品 質量份 5 6 8 4 5 6 7 8 聚碳酸酯 質量份 95 94 92 96 95 94 93 92 表面電阻 Ω/cm2 3.9Χ107 6.9Χ104 7.9x103 3.5xl06 2.2χ104 4.1χ105 1.9xl05 5.4xl04 體積電 阻値 Ωοπα 8.3x104 l.lxlO4 1.6xl03 1.2xl04 1.4χ103 8.4x10s 4.6x105 1.6xl04 總結上表2、表3所示結果，混合纖維徑分布不同之 兩種類之碳纖維而成者相較於僅使用粗徑品者，具體而言 爲對實施例2與比較例1、實施例4與比較例7、實施例5 與比較例9加以比較時，確認即使碳纖維在相同質量份 下，混合品者亦顯示比粗徑品良好之導電性。另一方面， 於實施例2與比較例4、實施例3與比較例6，於相同質 量份下細徑品者顯示良好之導電性。此係由於細徑品者於 φ 提高導電性方面有優異之傾向。然而，如上述可知，細徑 品之製造成本較高，朝樹脂中混練之際，黏性升高而難以 出現原本樹脂本來之物性。因此表2中，破斷延伸率於混 合品爲良好。混合品顯示充分之表面電阻値及體積電阻 値’且破斷延伸率在60%以上。因此該混合品可發揮樹脂 之力學特性與導電性賦予之均衡良好特性而可謂爲優異。 [實施例6及比較例1 0、1 1 ] 使實施例1中獲得之粗徑品之碳纖維構造體（比較例 -39- 201027565 1 ο)、細徑品之碳纖維構造體（比較例1 1)，或將該等之粗 徑品與細徑品之氣相碳纖維構造體以5 : 1之質量比混合 均質化而成之混合品（實施例6)之含量成爲2.0質量。/。之方 式，將0.22克之各碳纖維構造體分別調配於1〇克之環氧 樹脂（ADEKA RESIN EP4100E，環氧當量 190，ADEKA (股） 公司製造）、硬化劑（ADEKA Hardner EH3636-AS，ADEKA(股） 公司製造）中，且以自轉-公轉型離心攪拌機（脫氣攪拌機 (商品名），AR-250，THINKY (股）製造），經10分鐘混練 後，調製用於測定黏度之碳纖維構造體之環氧樹脂混練 物。 使用高性能旋轉式流變計（Geminil50，Bhlin Instruments 製造），在溫度25°C，頻率範圍0.01~10Hz，自動應力模式 之下，測定比較例1 〇、比較例1 1及實施例6之碳纖維構 造體與環氧樹脂之 2.0質量％混合物之黏度（Complex Viscosity)。結果示於圖4。 由圖4可了解，混合品（實施例6)之環氧樹脂混合物 之黏度與粗徑品之環氧樹脂混合物（比較例1 〇)之黏度相 當，且比細徑品之環氧樹脂混合物（比較例1 1)之黏度低。 [產業上利用之可能性] 因此本發明之導電性樹脂複合材在〇A設備領域、電 器電子設備領域等之各種工業用途中極爲有用’其所能達 成之工業效果極大。 -40- 201027565 【圖式簡單說明】 圖1爲說明提高破斷延伸之機構之圖面。 圖2爲模示性顯示本實施形態中之碳纖維製造裝置之 構造之構造圖。 圖3爲（粗徑品：細徑品=5 : 1(質量比））混合粉體之 SEM照片。 圖4爲顯示本發明相關之黏度測定結果之作圖。 【主要元件符號說明】 1 :碳纖維之製造裝置 2 :原料槽 3 :原料導入管 4 :氣體槽 5 :氣體導入管 6 :蒸發器 〇 7:原料混合氣體導入管 8 :反應爐 9 :導入噴嘴 10:整流·緩衝板 11 :加熱機構 12 :碳纖維回收器 13 :氣體排出管 141原料混合氣體導入口 15 :冷卻氣體導入口 -41 - 201027565 1 6 :冷卻氣體出口 20:金屬觸媒粒子生成帶域 30:碳纖維製造帶域 -42-The apparatus was a universal material testing machine (Intesco 2005-5 type) with a test speed of 50 mm/min and a distance between the clamps of 115 mm, which was carried out under a test environment of 23 ° C and 50% RH. The average enthalpy of the breaking elongation 値 of the five test pieces measured was measured in the same manner as above. The results obtained are shown in Table 2. (3) Erosion property 2000 ml of ultrapure water was poured into a 3000 ml glass beaker which was washed with ultrapure water, and a test piece (50 x 90 x 3 mm) which was injection molded was dipped. Subsequently, ultrasonic waves were applied for 1 minute at 5210E-DTH (47 kHz/140 W) (trade name, manufactured by BRANSON Co., Ltd.). Subsequently, the extracted ultrapure water was sucked by a liquid microparticle measuring instrument HIAC ROYCO SYSTEM 801 1 (trade name, manufactured by HACH ULTRA AN ALYTIC S Co., Ltd.), and the amount of dust generated by dust particles having a diameter of 0.5 μm or more was measured. The results obtained are shown in Table 2. [Table 2] Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Fine carbon fiber type mixed product Large diameter diameter Large diameter diameter Small diameter average diameter Fiber diameter (nm) 102 117 117 58 58 Fiber diameter standard Deviation 36 26 26 13 13 Parts by mass 6.38 6.38 7.53 4.17 6.38 Polycarbonate parts by mass 100 100 100 100 100 Surface resistance Ω/cm2 2.75χ1〇5 6.33X106 1.38x10s 5.08x105 5.23x103 Breaking elongation % 60 40 32 27.1 22 Exfoliation - 〇〇〇〇〇 ※ Mixed product... Small diameter product: Thick diameter product = 1: 5 (mass ratio) * Ejection resistance 〇. 5μηι or more dust emission amount is 5,000 / cm2 as a reference 値 ( Specification 値), and the following is judged as 〇. 201027565 [Table 3] Example 3 Example 4 Example 5 Comparative Example 5 Comparative Example ό Comparative Example 7 Comparative Example 8 Comparative Example 9 Fine carbon fiber type mixed product mixed product mixture small diameter product small diameter large diameter large diameter product Thick diameter products: 2:3 (mass ratio) 1:2 (mass ratio) 3:5 (mass ratio) Only small diameter products only have large diameters, only large diameters, only large diameters, only large diameters Parts by mass 5 6 8 4 5 6 7 8 Polycarbonate parts by mass 95 94 92 96 95 94 93 92 Surface resistance Ω/cm2 3.9Χ107 6.9Χ104 7.9x103 3.5xl06 2.2χ104 4.1χ105 1.9xl05 5.4xl04 Volume resistance 値Ωοπα 8.3 X104 l.lxlO4 1.6xl03 1.2xl04 1.4χ103 8.4x10s 4.6x105 1.6xl04 Summarize the results shown in Table 2 and Table 3, the two types of carbon fiber with different mixed fiber diameter distribution are compared with those with only coarse diameter. Specifically, when Comparing Example 2 with Comparative Example 1, Example 4, Comparative Example 7, Example 5, and Comparative Example 9, it was confirmed that even if the carbon fibers were in the same mass portion, the mixed product showed a specific diameter. Good electrical conductivity. On the other hand, in Example 2, Comparative Example 4, Example 3, and Comparative Example 6, a good diameter was exhibited in the same mass portion. This is because the small diameter product has an excellent tendency to improve conductivity in φ. However, as described above, the production cost of the small-diameter product is high, and when the resin is kneaded in the resin, the viscosity is increased and it is difficult to exhibit the original physical properties of the original resin. Therefore, in Table 2, the breaking elongation was good in the mixed product. The mixture showed sufficient surface resistance 体积 and volume resistance 値' and the elongation at break was 60% or more. Therefore, the mixed product exhibits excellent balance between the mechanical properties of the resin and the conductivity imparting property. [Example 6 and Comparative Example 1 0, 1 1] The carbon fiber structure (Comparative Example-39-201027565 1) of the large diameter product obtained in Example 1 and the carbon fiber structure of the narrow diameter product (Comparative Example 1 1) The content of the mixed product (Example 6) in which the coarse-diameter product and the gas-phase carbon fiber structure of the small-diameter product were homogenized in a mass ratio of 5:1 was 2.0 mass. /. In this manner, 0.22 g of each carbon fiber structure was separately prepared in an epoxy resin (ADEKA RESIN EP4100E, epoxy equivalent 190, manufactured by ADEKA Co., Ltd.), and hardener (ADEKA Hardner EH3636-AS, ADEKA) Manufactured by the company, and rotated by a self-rotating-common-transformation centrifugal mixer (degassing mixer (trade name), AR-250, THINKY (manufactured)), after 10 minutes of mixing, the ring of carbon fiber structure for measuring viscosity is prepared. Oxygen resin kneaded material. The carbon fibers of Comparative Example 1 〇, Comparative Example 1 1 and Example 6 were measured using a high-performance rotary rheometer (Geminil 50, manufactured by Bhlin Instruments) at a temperature of 25 ° C and a frequency range of 0.01 to 10 Hz in an automatic stress mode. The viscosity of the 2.0% by mass mixture of the structure and the epoxy resin (Complex Viscosity). The results are shown in Figure 4. As can be seen from Fig. 4, the viscosity of the epoxy resin mixture of the mixed product (Example 6) is equivalent to that of the epoxy resin mixture of the large diameter product (Comparative Example 1), and the epoxy resin mixture of the fine diameter product ( Comparative Example 1 1) has a low viscosity. [Industrial Applicability] The conductive resin composite of the present invention is extremely useful in various industrial applications such as the field of 〇A equipment and the field of electrical and electronic equipment, and the industrial effect that can be achieved is extremely large. -40- 201027565 [Simple description of the drawing] Fig. 1 is a view showing the mechanism for improving the breaking extension. Fig. 2 is a structural view schematically showing the structure of a carbon fiber manufacturing apparatus in the embodiment. Fig. 3 is a SEM photograph of a mixed powder of (a large diameter product: a small diameter product = 5:1 (mass ratio)). Fig. 4 is a graph showing the results of viscosity measurement of the present invention. [Description of main component symbols] 1 : Carbon fiber manufacturing apparatus 2 : Raw material tank 3 : Raw material introduction pipe 4 : Gas tank 5 : Gas introduction pipe 6 : Evaporator 〇 7 : Raw material mixed gas introduction pipe 8 : Reaction furnace 9 : Introduction nozzle 10: rectification/buffer plate 11 : heating mechanism 12 : carbon fiber recovery device 13 : gas discharge pipe 141 raw material mixed gas introduction port 15 : cooling gas introduction port - 41 - 201027565 1 6 : cooling gas outlet 20 : metal catalyst particle generation zone Field 30: Carbon Fiber Manufacturing Band -42-