TWI443149B - Conductive resin composites - Google Patents

Description

導電性樹脂複合材料 Conductive resin composite

本發明係關於一種導電性樹脂複合材料。 The present invention relates to a conductive resin composite material.

包含樹脂與導電性填充料之導電性樹脂複合材料在半導體領域、電氣設備相關領域、汽車．航空領域中被廣泛使用，其主要目的可列舉：保護半導體零件不受靜電影響、藉由阻斷電磁波而防止精密機器之誤動作、防止伴隨摩擦之靜電˙發熱等。作為半導體領域等中所使用之導電性樹脂複合材料之母材樹脂，廣泛使用聚碳酸酯，其原因可列舉為：由粒子引起之污染少、逸氣少、表面整飾以及光澤良好、流動性優異、翹曲少、回收再利用/重複使用性優異等，聚碳酸酯具有之優異之樹脂特性。尤其自環境負荷之問題、或成本削減方面等考慮，該優異之回收再利用/重複使用性被廣泛認為係有效之物性。 Conductive resin composite materials containing resin and conductive filler in the field of semiconductors, electrical equipment, automotive. It is widely used in the field of aviation, and its main objects are to protect semiconductor parts from static electricity, to prevent malfunction of precision machines by blocking electromagnetic waves, and to prevent static electricity and heat accompanying friction. Polycarbonate is widely used as a base resin for a conductive resin composite material used in the semiconductor field and the like, and the reason for this is that there is less contamination by particles, less outgassing, surface finishing and gloss, and fluidity. Excellent in properties, low warpage, excellent recycling and reusability, and polycarbonate, which has excellent resin properties. Especially in terms of environmental load problems or cost reduction, such excellent recycling/reuseability is widely considered to be effective physical properties.

另一方面，作為對母材樹脂賦予導電性之方法，有在樹脂中添加賦予離子傳導性之材料，或添加金屬微粒子、金屬纖維、碳微粒子、碳纖維等導電性填充料之方法。其中，自性能、環境問題等方面考慮，使用碳系材料來賦予導電性正逐漸成為主流。 On the other hand, as a method of imparting conductivity to the base resin, a method of adding a material that imparts ion conductivity to the resin or adding a conductive filler such as metal fine particles, metal fibers, carbon fine particles, or carbon fibers may be added. Among them, from the viewpoints of performance and environmental problems, the use of carbon-based materials to impart conductivity is gradually becoming mainstream.

然而，於為了展現必需之導電性而使用粒徑為數μm之碳粒子之情形時，必需相對於樹脂100質量份而添加40~50質量份之上述碳粒子，科琴黑(Ketjen black)等碳黑亦必需添加8~15質量份，如此之複合材料化與原本之樹脂相比 較，會引起黏度上升˙流動性下降、或硬度上升等物性變化。結果，成為成形加工時之模具轉印性、光澤等外觀不良或耐衝擊性下降之原因。碳纖維於添加30質量份之條件下亦可獲得體積固有電阻率為10²Ωcm之導電性，但仍因添加量多而導致流動性之惡化等。 However, when carbon particles having a particle diameter of several μm are used in order to exhibit the necessary conductivity, it is necessary to add 40 to 50 parts by mass of the above carbon particles, carbon such as Ketjen black, to 100 parts by mass of the resin. Black must also be added in an amount of 8 to 15 parts by mass. Such a composite material may cause a change in viscosity, a decrease in fluidity, or a change in physical properties such as a rise in hardness as compared with the original resin. As a result, it is a cause of poor appearance such as mold transfer property and glossiness during molding processing, and deterioration in impact resistance. The carbon fiber can also obtain a conductivity having a volume specific resistivity of 10 ² Ωcm under the condition of adding 30 parts by mass, but the fluidity is deteriorated due to the addition amount.

近年來，作為如上所述之導電性填充料，正使用氣相成長碳纖維(vapor grown carbon fiber)。氣相成長碳纖維係利用氣相法合成之微細碳纖維，基本上係包含連續之6員環碳結構之石墨片單層或者多層地形成之管狀結構者。又，其係纖維直徑為奈米級、長度為微米級、且以高的縱橫比為一特徵之導電性填充材料。已報導有，若使用該氣相成長碳纖維，則自其高導電性而言，藉由對樹脂100質量份添加數質量份之該氣相成長碳纖維即獲得具有所需導電性之樹脂複合材料(專利文獻1、2)。 In recent years, as the conductive filler as described above, a vapor grown carbon fiber is being used. The vapor-grown carbon fiber is a fine carbon fiber synthesized by a vapor phase method, and is basically a tubular structure in which a graphite sheet of a continuous 6-membered ring carbon structure is formed in a single layer or a plurality of layers. Further, it is a conductive filler having a fiber diameter of a nanometer order, a micrometer-scale length, and a high aspect ratio. It has been reported that, when the vapor-grown carbon fiber is used, a resin composite material having a desired conductivity can be obtained by adding several parts by mass of the vapor-grown carbon fiber to 100 parts by mass of the resin (for high conductivity) ( Patent Documents 1, 2).

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本專利特開2006-306960號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-306960

專利文獻2：日本專利特開2006-225648號公報 Patent Document 2: Japanese Patent Laid-Open No. 2006-225648

但是，於包含聚碳酸酯與氣相成長碳纖維之導電性樹脂複合材料中，若直至賦予良好導電性之程度為止將氣相成長碳纖維添加於聚碳酸酯中，與其相反，斷裂伸長率等樹脂複合材料之物性˙成形性下降，成為使用該樹脂複合材料來形成目標成形物時之問題。又，氣相成長碳纖維之纖維直徑極細，亦有由熔融之聚碳酸酯樹脂所引起的氣相成 長碳纖維表面之潤濕性惡化等，從而導致氣相成長碳纖維自成形之樹脂複合材料脫落。尤其於半導體領域中，此成為半導體製品之故障˙損壞之原因而被視為問題。即，需要有具備良好之導電性、聚碳酸酯本來所具有之優異之成形性等樹脂特性以及氣相成長碳纖維之低脫落性等任一者均為充分程度之導電性樹脂複合材料。 However, in a conductive resin composite material containing a polycarbonate and a vapor-grown carbon fiber, a vapor-grown carbon fiber is added to a polycarbonate until a good conductivity is imparted, and a resin composite such as elongation at break is reversed. Material properties of the material The mold formability is lowered, which is a problem when the resin composite material is used to form a target molded product. Moreover, the diameter of the fiber of the vapor-grown carbon fiber is extremely fine, and there is also a vapor phase formed by the molten polycarbonate resin. The wettability of the surface of the long carbon fiber is deteriorated, and the vapor-grown carbon fiber is peeled off from the formed resin composite material. Especially in the field of semiconductors, this is considered to be a cause of failure and damage of semiconductor products. In other words, it is necessary to have a conductive resin composite material having sufficient conductivity, resin properties such as excellent formability of polycarbonate, and low peeling property of vapor-grown carbon fibers.

本發明之目的在於提供一種不僅保持良好之導電性，並且氣相成長碳纖維之脫落少，且與成形性相關之斷裂伸長率得到改善之導電性樹脂複合材料。 An object of the present invention is to provide a conductive resin composite material which not only maintains good electrical conductivity, but also has less peeling of vapor-grown carbon fibers and improved elongation at break in terms of formability.

本發明者們為了解決上述問題而進行潛心研究，結果發現以下知識見解。 The present inventors conducted intensive studies to solve the above problems, and as a result, found the following knowledge.

即，本發明之導電性樹脂複合材料係含有聚碳酸酯樹脂以及氣相成長碳纖維者，氣相成長碳纖維之平均纖維外徑為超過100nm且150nm以下，聚碳酸酯樹脂與氣相成長碳纖維之含量為，相對於聚碳酸酯樹脂100質量份，該氣相成長碳纖維為1~11.2質量份，並且該導電性樹脂複合材料之斷裂伸長率為30%以上。如上所述之導電性樹脂複合材料表現出良好之導電性，並且氣相成長碳纖維自導電性樹脂複合材料之脫落亦少，且成形性良好。 That is, the conductive resin composite material of the present invention contains a polycarbonate resin and a vapor-grown carbon fiber, and the average fiber outer diameter of the vapor-grown carbon fiber is more than 100 nm and 150 nm or less, and the content of the polycarbonate resin and the vapor-grown carbon fiber. The vapor-grown carbon fiber is 1 to 11.2 parts by mass based on 100 parts by mass of the polycarbonate resin, and the elongation at break of the conductive resin composite material is 30% or more. The conductive resin composite material as described above exhibits good electrical conductivity, and the vapor-grown carbon fiber is less detached from the conductive resin composite material, and the moldability is good.

又，本發明中，氣相成長碳纖維之纖維外徑的分布之標準偏差為25~40nm，較好的是30~40nm即可。於氣相成長 碳纖維之纖維外徑在如上所述之標準偏差範圍內之情形時，使用氣相成長碳纖維之導電性樹脂複合材料之斷裂伸長率變得良好。 Further, in the present invention, the standard deviation of the distribution of the outer diameter of the fiber of the vapor-grown carbon fiber is 25 to 40 nm, preferably 30 to 40 nm. Growing in the vapor phase When the outer diameter of the fiber of the carbon fiber is within the standard deviation range as described above, the elongation at break of the conductive resin composite using the vapor-grown carbon fiber becomes good.

又，較好的是，氣相成長碳纖維(微細碳纖維)形成三維網狀之氣相成長碳纖維結構體，該氣相成長碳纖維結構體係具有複數個粒狀部且纖維直徑較各個粒狀部之外徑更細的氣相成長碳纖維自該粒狀部延伸出複數個之態樣，並且該粒狀部係於該氣相成長碳纖維之成長過程中形成者。 即，較好的是氣相成長碳纖維結合複數個粒狀部而形成表現出網狀結構之氣相成長碳纖維結構體。藉由具有如上所述之立體結構，一般認為較氣相成長碳纖維之外徑更大之粒狀部於導電性樹脂複合材料之聚碳酸酯樹脂之基質中發揮物理性定錨效應(anchor effect)，而減少氣相成長碳纖維自導電性樹脂複合材料之脫落。 Further, it is preferred that the vapor-grown carbon fibers (fine carbon fibers) form a three-dimensional network of vapor-phase-grown carbon fiber structures having a plurality of granular portions and having a fiber diameter smaller than each of the granular portions The gas-growth carbon fiber having a finer diameter extends from the granular portion to a plurality of forms, and the granular portion is formed during the growth of the vapor-grown carbon fiber. That is, it is preferred that the vapor-grown carbon fiber is bonded to a plurality of granular portions to form a vapor-phase-grown carbon fiber structure exhibiting a network structure. By having the three-dimensional structure as described above, it is considered that the granule portion having a larger outer diameter than the vapor-grown carbon fiber exhibits a physical anchor effect in the matrix of the polycarbonate resin of the conductive resin composite material. And reducing the shedding of the vapor-grown carbon fiber from the conductive resin composite.

又，本發明提供一種以氣相成長碳纖維(微細碳纖維)自導電性複合材料之脫落減少為特徵的導電性複合材料。即，將寬度為50mm、長度為90mm、厚度為3mm之導電性樹脂複合材料浸漬於超純水2000mL中，施加47kHz之超音波60秒時，自表面脫落之粒徑為0.5μm以上之脫落物之數量於每單位表面積中為5000個/cm²以下。若脫落物之數量為如上所述，例如於本發明在半導體領域中使用之情形時，可抑制由脫落物引起之半導體製品之故障˙損壞。 Further, the present invention provides a conductive composite material characterized by a reduction in the fall-off of a vapor-grown carbon fiber (fine carbon fiber) from a conductive composite material. In other words, the conductive resin composite material having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm was immersed in 2000 mL of ultrapure water, and when the ultrasonic wave of 47 kHz was applied for 60 seconds, the particle size falling off from the surface was 0.5 μm or more. The amount is 5,000 / cm ² or less per unit surface area. If the amount of the detached material is as described above, for example, in the case where the present invention is used in the field of semiconductors, it is possible to suppress malfunction and damage of the semiconductor article caused by the detachment.

較好的是粒狀部具有氣相成長碳纖維之平均纖維外徑之 1.3倍以上之平均的與圓相當之外徑。藉此，可帶來氣相成長碳纖維相互之間的牢固結合。 It is preferred that the granular portion has an average fiber outer diameter of the vapor-grown carbon fiber. An average diameter of 1.3 times or more equal to the outer diameter of the circle. Thereby, a strong bond between the vapor-grown carbon fibers can be brought about.

較好的是使用導電性樹脂複合材料而成形之成形物的表面電阻值為10³~10¹²Ω/□。若使用具有如上所述之表面電阻值的成形物，可保護精密半導體零件不受靜電之破壞。 It is preferred that the molded article formed by using the conductive resin composite material has a surface resistance value of 10 ³ to 10 ¹² Ω/□. If a molded article having the surface resistance value as described above is used, the precision semiconductor component can be protected from static electricity.

更好的是導電性樹脂複合材料之斷裂伸長率為40%以上(進而好的是50%以上)。藉此，使用導電性樹脂複合材料來射出成形等製造成形物時的成形性可進一步提高。 More preferably, the conductive resin composite has an elongation at break of 40% or more (and more preferably 50% or more). Thereby, the moldability at the time of producing a molded article, such as injection molding, using a conductive resin composite material can be further improved.

氣相成長碳纖維係包含平均纖維外徑為超過5nm且100nm以下之氣相成長碳纖維A與平均纖維外徑為超過100nm且200nm以下之氣相成長碳纖維B的混合物，較好的是該混合物中之氣相成長碳纖維B之質量大於氣相成長碳纖維A之質量。藉此，變得容易滿足上述之平均纖維外徑與纖維外徑分布之標準偏差範圍，導電性樹脂複合材料之斷裂伸長率變得更良好。 The vapor-grown carbon fiber is a mixture of a vapor-grown carbon fiber A having an average fiber outer diameter of more than 5 nm and 100 nm or less and a vapor-grown carbon fiber B having an average fiber outer diameter of more than 100 nm and 200 nm or less, preferably in the mixture. The mass of the vapor grown carbon fiber B is greater than the mass of the vapor grown carbon fiber A. Thereby, the standard deviation range of the average fiber outer diameter and the fiber outer diameter distribution described above is easily satisfied, and the elongation at break of the conductive resin composite material is further improved.

再者，導電性樹脂複合材料可將聚碳酸酯樹脂與氣相成長碳纖維(微細碳纖維)於該聚碳酸酯樹脂之熔融點以上之溫度條件下加以混練而製造。 Further, the conductive resin composite material can be produced by kneading a polycarbonate resin and a vapor-grown carbon fiber (fine carbon fiber) at a temperature higher than a melting point of the polycarbonate resin.

依據本發明，可提供一種不僅保持良好之導電性，並且氣相成長碳纖維之脫落少，且與成形性相關之斷裂伸長率得到改善之導電性樹脂複合材料。 According to the present invention, it is possible to provide a conductive resin composite material which not only maintains good electrical conductivity, but also has less peeling of vapor-phase-grown carbon fibers and improved elongation at break in terms of formability.

以下，基於較好之實施形態對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail based on preferred embodiments.

本發明中用作導電性樹脂複合材料之母材的聚碳酸酯樹脂係藉由使各種二羥基二芳基化合物與光氣進行反應之光氣法、或者使二羥基二芳基化合物與碳酸二苯基酯等碳酸酯進行反應之酯交換法而獲得之聚合物，作為代表性者，可列舉由2,2-雙(4-羥基苯基)丙烷(雙酚A)製造之聚碳酸酯樹脂。 The polycarbonate resin used as a base material of the conductive resin composite material in the present invention is a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a dihydroxydiaryl compound and a carbonic acid A polymer obtained by a transesterification method in which a carbonate such as a phenyl ester is subjected to a reaction, and a polycarbonate resin produced from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is exemplified. .

作為上述二羥基二芳基化合物，除雙酚A以外，可列舉：如雙(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丁烷、2,2-雙(4-羥基苯基)辛烷、雙(4-羥基苯基)苯基甲烷、2,2-雙(4-羥基苯基-3-甲基苯基)丙烷、1,1-雙(4-羥基-3-第三丁基苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷等的雙(羥基芳基)烷烴類，如1,1-雙(4-羥基苯基)環戊烷、1,1-雙(4-羥基苯基)環己烷等的雙(羥基芳基)環烷烴類，如4,4'-二羥基二苯基醚、4,4'-二羥基-3,3'-二甲基二苯基醚等的二羥基二芳基醚類，如4,4'-二羥基二苯基硫醚等的二羥基二芳基硫醚類，如4,4'-二羥基二苯基亞碸、4,4'-二羥基-3,3'-二甲基二苯基亞碸等的二羥基二芳基亞碸類，如4,4'-二羥基二苯基碸、4,4'-二羥基-3,3'-二甲基二苯基碸等的二羥基二芳基碸類等。 As the above dihydroxydiaryl compound, in addition to bisphenol A, there may be mentioned, for example, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis ( 4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3- Methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2- a bis(hydroxyaryl)alkane such as bis(4-hydroxy-3,5-dibromophenyl)propane or 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, such as 1 a bis(hydroxyaryl)cycloalkane such as 1-bis(4-hydroxyphenyl)cyclopentane or 1,1-bis(4-hydroxyphenyl)cyclohexane, such as 4,4'-dihydroxy Dihydroxydiaryl ethers such as diphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, such as 4,4'-dihydroxydiphenyl sulfide Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxy-3,3'-dimethyldiphenylarylene, etc. A quinone quinone, such as a dihydroxy diaryl fluorene such as 4,4'-dihydroxydiphenyl fluorene or 4,4'-dihydroxy-3,3'-dimethyldiphenyl hydrazine.

該等可單獨或者混合2種以上使用，進而，亦可將上述二羥基二芳基化合物與如以下所示之3價以上之酚化合物混合使用。 These may be used singly or in combination of two or more kinds. Further, the dihydroxydiaryl compound may be used in combination with a valent or higher phenol compound as shown below.

作為3價以上之酚，可列舉：間苯三酚、4,6-二甲基- 2,4,6-三-(4-羥基苯基)-庚烯、4,6-二甲基-2,4,6-三-(4-羥基苯基)-庚烷、1,3,5-三-(4-羥基苯基)-苯、1,1,1-三-(4-羥基苯基)-乙烷以及2,2-雙-[4,4-(4,4'-二羥基聯苯基)環己基]-丙烷等。 Examples of the phenol having a trivalent or higher value include phloroglucinol and 4,6-dimethyl group. 2,4,6-tris-(4-hydroxyphenyl)-heptene, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptane, 1,3, 5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxyphenyl)-ethane and 2,2-bis-[4,4-(4,4'-- Dihydroxybiphenyl)cyclohexyl]-propane and the like.

聚碳酸酯樹脂之黏度平均分子量通常為10000~100000，較好的是15000~35000，進而好的是17000~28000。 The viscosity average molecular weight of the polycarbonate resin is usually from 10,000 to 100,000, preferably from 15,000 to 35,000, and further preferably from 17,000 to 28,000.

本發明中所使用之氣相成長碳纖維較好的是平均纖維外徑為超過100nm且150nm以下，更好的是105nm~145nm，進而好的是110nm~140nm。若氣相成長碳纖維之平均纖維外徑為100nm以下，則包含該氣相成長碳纖維與聚碳酸酯樹脂之導電性樹脂複合材料的斷裂伸長率為30%以下，從而，使用該樹脂複合材料來射出成形等製造成形物時的成形性下降。一般認為其原因在於，由於平均纖維外徑為100nm以下之氣相成長碳纖維與平均纖維外徑超過100nm之氣相成長碳纖維相比較，向母材樹脂中添加相同質量份之情形時的碳纖維之根數變多，故而阻礙導電性樹脂複合材料之斷裂伸長率。另一方面，若平均纖維外徑超過150nm，則樹脂複合材料每單位體積之氣相成長碳纖維之根數變得極少，因此少量添加時導電路徑變得難以形成，無法獲得導電性良好之樹脂複合材料。 The vapor-grown carbon fiber used in the present invention preferably has an average fiber outer diameter of more than 100 nm and 150 nm or less, more preferably 105 nm to 145 nm, and further preferably 110 nm to 140 nm. When the average fiber outer diameter of the vapor-grown carbon fiber is 100 nm or less, the conductive resin composite material containing the vapor-grown carbon fiber and the polycarbonate resin has an elongation at break of 30% or less, and is used to emit the resin composite material. The moldability at the time of producing a molded article such as molding is lowered. It is considered that the reason is that the carbon fiber root is added to the base resin in the case where the same mass portion is added to the vapor-grown carbon fiber having an average fiber outer diameter of 100 nm or less and the average fiber outer diameter exceeding 100 nm. Since the number is increased, the elongation at break of the conductive resin composite material is hindered. On the other hand, when the average fiber outer diameter exceeds 150 nm, the number of vapor-grown carbon fibers per unit volume of the resin composite material is extremely small. Therefore, the conductive path becomes difficult to form when a small amount is added, and a resin composite having good conductivity cannot be obtained. material.

為了測定此處所使用之平均纖維外徑，首先利用經設定為倍率35000倍之掃描式電子顯微鏡對測定對象氣相成長碳纖維，隨機攝影至少3視野以上。然後，對各攝影視野中可測定之纖維外徑全部進行測定，以使纖維外徑之測定 點數合計超過50點，對其進行數量平均即可。本發明之導電性樹脂複合材料中所使用之氣相成長碳纖維在該方法之每1視野中，可測定約20~50點之纖維外徑。再者，於包含粒狀部之氣相成長碳纖維結構體中的氣相成長碳纖維之情形時，並非以該結構體中之粒狀部，而是以氣相成長碳纖維之外徑來作為上述纖維外徑。 In order to measure the average fiber outer diameter used here, the gas-phase-grown carbon fiber to be measured is firstly imaged by a scanning electron microscope set to a magnification of 35,000 times, and at least three fields of view are randomly photographed. Then, all the outer diameters of the fibers measurable in each photographic field of view are measured to determine the outer diameter of the fibers. The total number of points exceeds 50 points, and the number can be averaged. The vapor-grown carbon fiber used in the conductive resin composite material of the present invention can measure the fiber outer diameter of about 20 to 50 points per field of view of the method. Further, in the case of a vapor-grown carbon fiber in a vapor-phase-grown carbon fiber structure including a granular portion, the outer diameter of the vapor-grown carbon fiber is not used as the fiber in the structure. Outer diameter.

氣相成長碳纖維之纖維外徑的分布之標準偏差較好的是25~40nm，更好的是30~40nm。使用標準偏差為25~40nm之氣相成長碳纖維的導電性樹脂複合材料，一般表現出30%以上之斷裂伸長率，若使用標準偏差為30~40nm之氣相成長碳纖維，則一般表現出50%以上之斷裂伸長率。一般認為其原因在於，後述呈三維網狀結構體之氣相成長碳纖維中，處於該標準偏差範圍中所規定之纖維外徑之分佈範圍中的粗纖維外徑之氣相成長碳纖維與細纖維外徑之氣相成長碳纖維，對使用該氣相成長碳纖維之導電性樹脂複合材料之斷裂伸長率施加互補之效果。 The standard deviation of the distribution of the outer diameter of the fiber of the vapor-grown carbon fiber is preferably 25 to 40 nm, more preferably 30 to 40 nm. Conductive resin composites using a vapor-grown carbon fiber with a standard deviation of 25 to 40 nm generally exhibit an elongation at break of 30% or more. If a vapor-grown carbon fiber with a standard deviation of 30 to 40 nm is used, it generally exhibits 50%. The above elongation at break. It is considered that the reason is that, in the vapor-grown carbon fiber which is a three-dimensional network structure described later, the outer diameter of the coarse fiber in the distribution range of the outer diameter of the fiber specified in the standard deviation range is vapor-grown carbon fiber and fine fiber. The vapor-grown carbon fiber of the diameter exerts a complementary effect on the elongation at break of the conductive resin composite material using the vapor-grown carbon fiber.

又，較好的是氣相成長碳纖維形成與複數個粒狀部結合之網狀結構之氣相成長碳纖維結構體。如上所述之結構中，複數個粒狀部相互之間以複數個氣相成長碳纖維相互立體地結合，因此並非平面之分支結構，而是具有三維擴展。 Further, it is preferred that the vapor-grown carbon fibers form a vapor-grown carbon fiber structure having a network structure in combination with a plurality of granular portions. In the structure as described above, the plurality of granular portions are sterically joined to each other by a plurality of vapor-grown carbon fibers, and thus are not a planar branched structure but have a three-dimensional expansion.

又，粒狀部係於氣相成長碳纖維之成長過程中形成者。因此，複數個粒狀部與氣相成長碳纖維並非藉由結著劑等(包括碳物質者)之僅於外觀上連接，而是兩者部分性共有 相同之多層結構之石墨片。藉此，粒狀部與氣相成長碳纖維牢固結合。 Further, the granular portion is formed during the growth of the vapor-grown carbon fiber. Therefore, the plurality of granular portions and the vapor-grown carbon fibers are not only externally connected by a bonding agent or the like (including a carbonaceous substance), but are partially shared by the two. The same multilayer graphite sheet. Thereby, the granular portion is firmly bonded to the vapor-grown carbon fiber.

對於更牢固之結合而言較為理想之粒狀部之平均的與圓相當之外徑為氣相成長碳纖維之平均纖維外徑之1.3倍以上，更好的是1.5倍以上且5倍以下。堅固之氣相成長碳纖維藉由如此牢固之結合而形成為網狀的氣相成長碳纖維結構體，即使藉由混練等而添加於聚碳酸酯中，其結構體亦得以保持。一般認為如上所述之網狀結構於導電性樹脂複合材料之聚碳酸酯樹脂之基質中發揮物理性定錨效應，因而如後文所述使該氣相成長碳纖維自該導電性樹脂複合材料之脫落減少。 The average outer diameter of the granular portion which is more preferable for the stronger bonding is 1.3 times or more, more preferably 1.5 times or more and 5 times or less the average outer diameter of the vapor-grown carbon fibers. The vapor-grown carbon fiber structure in which the solid gas-phase-growth carbon fiber is formed into a network by such a strong bond is maintained even if it is added to the polycarbonate by kneading or the like. It is considered that the network structure as described above exerts a physical anchoring effect in the matrix of the polycarbonate resin of the conductive resin composite material, and thus the vapor-grown carbon fiber is made from the conductive resin composite material as will be described later. Reduced shedding.

再者，本說明書中所謂之「粒狀部之平均的與圓相當之外徑」，係指測定經觀察之粒狀部之面積，作為一個正圓而求出直徑的值。具體而言，係以電子顯微鏡對氣相成長碳纖維相互之結合點即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件，例如WinRoof(商品名，三谷商事股份有限公司製造)來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與圓相當之直徑，並加以平均而得者。 In the present specification, the "outer diameter of the granular portion corresponding to the outer diameter" means a value obtained by measuring the area of the observed granular portion and determining the diameter as a perfect circle. Specifically, an electron microscope is used to image the junction of the vapor-grown carbon fibers, that is, the shape of the granular portion, and an appropriate image analysis software such as WinRoof (trade name, Sangu Trading Co., Ltd.) is used in the photographic image. The company's profile is used to trace the outline of each granular part, and the area within the outline is obtained. Based on this area, the diameter corresponding to the circle of each granular part is calculated and averaged.

又，上述氣相成長碳纖維結構體較理想的是面積基準之平均的與圓相當之直徑為20~100μm。此處所謂面積基準之平均的與圓相當之直徑，係指使用電子顯微鏡等對氣相成長碳纖維結構體之外形進行攝影，在該攝影圖像中，與上述同樣，使用適當之圖像分析軟件來描出各氣相成長碳 纖維結構體之輪廓，求出輪廓內之面積，計算出各纖維結構體之與圓相當之直徑，並將其平均化而得者。該平均的與圓相當之直徑係成為判斷經調配於聚碳酸酯樹脂之基質中時的該氣相成長碳纖維結構體之纖維長度的要因。概括而言，若平均的與圓相當之直徑小於20μm，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，若為超過100μm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。 Further, it is preferable that the vapor-phase-growth carbon fiber structure has an average area-to-circle diameter of 20 to 100 μm. Here, the average diameter of the area reference is equivalent to a circle, and the shape of the vapor-grown carbon fiber structure is photographed using an electron microscope or the like. In the photographic image, appropriate image analysis software is used as described above. To describe the vapor phase growth carbon The outline of the fiber structure is obtained, and the area in the outline is obtained, and the diameter corresponding to the circle of each fiber structure is calculated and averaged. The average diameter corresponding to the circle is a factor for determining the fiber length of the vapor-grown carbon fiber structure when it is formulated in a matrix of a polycarbonate resin. In general, if the average diameter corresponding to the 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 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.

進而，上述氣相成長碳纖維結構體具有氣相成長碳纖維疏鬆存在之蓬鬆結構，具體而言，較好的是其鬆密度為0.001~0.05g/cm³者，更好的是0.001~0.02g/cm³者。若為鬆密度超過0.05g/cm³者，則變得難以藉由少量添加來改善聚碳酸酯樹脂之物性。另一方面，若為鬆密度小於0.001g/cm³者，則所用量之氣相成長碳纖維之體積過度變高，藉由與聚碳酸酯樹脂混合而製備複合材料時變得難以操作等，對操作性產生不良影響。 Further, the vapor-phase-grown carbon fiber structure has a bulky structure in which a vapor-grown carbon fiber is loosely formed, and specifically, a bulk density of 0.001 to 0.05 g/cm ^{3 is} preferred, and more preferably 0.001 to 0.02 g/ Cm ³ person. If the bulk density exceeds 0.05 g/cm ³ , it becomes difficult to improve the physical properties of the polycarbonate resin by a small amount of addition. On the other hand, if the bulk density is less than 0.001g / cm ³ were, the bulk of the vapor-grown carbon fibers as the amount becomes excessively high, when the composite is prepared by the polycarbonate resin are mixed and the like becomes difficult to handle, for Operationality has an adverse effect.

又，上述氣相成長碳纖維結構體由於粒狀部與氣相成長碳纖維部分性共有相同之多層結構之石墨片，故而結構體自身之電特性等亦係非常優異者。作為本發明中所使用者，例如較好的是在一定壓縮密度0.8g/cm³下測定之粉末電阻值為0.005~0.025Ω˙cm以下者，更好的是0.005~0.020Ω˙cm。若為粉末電阻值超過0.025Ω˙cm者或小於0.005Ω˙cm者，則與聚碳酸酯樹脂進行複合材料化時，變得難 以製造可保持所需導電性之複合材料。 Further, in the vapor-phase-growing carbon fiber structure, since the granular portion and the vapor-phase-grown carbon fiber partially share the same multilayer graphite sheet, the electrical properties of the structure itself are excellent. As a user of the present invention, for example, it is preferred that the powder resistance value measured at a constant compression density of 0.8 g/cm ³ is 0.005 to 0.025 Ω ̇ cm or less, more preferably 0.005 to 0.020 Ω ̇ cm. If the powder resistance exceeds 0.025 Ω ̇cm or less than 0.005 Ω ̇cm, it becomes difficult to produce a composite material capable of maintaining desired conductivity when it is composited with a polycarbonate resin.

又，自欲賦予上述氣相成長碳纖維結構體較高之強度以及導電性之觀點而言，較理想的是構成氣相成長碳纖維之石墨片中之缺陷少。具體而言，例如較好的是利用拉曼光譜分析法(Raman spectroscopic analysis)測定之I_D/I_G比為0.2以下，更好的是0.1以下。拉曼光譜分析中，充分大之單結晶石墨僅出現1580cm^-1附近之波峰(G譜帶)。由於結晶為有限之微小尺寸或由於晶格缺陷，而於1360cm^-1附近出現波峰(D譜帶)。因此，若D譜帶與G譜帶之強度比(R=I₁₃₆₀/I₁₅₈₀=I_D/I_G)如上所述之特定值以下，則表示石墨片中之缺陷量少。 Further, from the viewpoint of imparting high strength and conductivity to the vapor-phase-grown carbon fiber structure, it is preferable that the graphite sheet constituting the vapor-grown carbon fiber has few defects. Specifically, for example, it is preferred that the I _D /I _G ratio measured by Raman spectroscopic analysis is 0.2 or less, more preferably 0.1 or less. In Raman spectroscopy, a sufficiently large single crystal graphite showed only a peak near the 1580 cm ^-1 (G band). A peak (D band) appears around 1360 cm ^-1 due to the finitely small size of the crystal or due to lattice defects. Therefore, if the intensity ratio of the D band to the G band (R = I ₁₃₆₀ / I ₁₅₈₀ = I _D / I _G ) is less than or equal to the specific value described above, it means that the amount of defects in the graphite sheet is small.

再者，此處所謂之缺陷，係指由於在構成氣相成長碳纖維之石墨片之排列中侵入碳原子以外之不要原子、或者必要之碳原子缺損、又或者產生偏移而產生的石墨片之排列之不完全部分(晶格缺陷(lattice defect))等。 In addition, the term "defect" as used herein refers to a graphite sheet which is produced by intrusion of carbon atoms other than carbon atoms in the arrangement of the graphite sheets constituting the vapor-phase-grown carbon fibers, or the necessary carbon atoms are missing or shifted. Incomplete part of the arrangement (lattice defect) and the like.

又，如上所述之包含聚碳酸酯以及氣相成長碳纖維之本申請案發明之導電性樹脂複合材料的斷裂伸長率較好的是30%以上，更好的是40%以上。若斷裂伸長率為30%以下，則衝擊強度以及對拉伸之韌性(黏著強度)下降，因此將此種導電性樹脂複合材料成形時形成較脆之成形物。 Further, the conductive resin composite material of the invention of the present invention comprising polycarbonate and vapor-grown carbon fibers as described above preferably has an elongation at break of 30% or more, more preferably 40% or more. When the elongation at break is 30% or less, the impact strength and the toughness (adhesive strength) against stretching are lowered. Therefore, when such a conductive resin composite material is molded, a brittle molded product is formed.

使用如上所述之導電性樹脂複合材料而成形之成形物，若其表面電阻值為10³~10¹²Ω/□，更好的是10⁶~10¹²Ω/□，則適合於用以保護精密半導體零件不受靜電破壞之零件容器、製造現場之地板材料等。尤其適合用於載帶等IC (integrated circuit，積體電路)零件包裝體或磁頭之搬送用托盤。其原因在於，自帶電之電子零件上不會引起靜電短路，而是於該容器側緩慢地除去。於容器之電阻值小於10⁶Ω/□之情形時，所蓄積之靜電急遽移動至該容器而產生放電現象，由此導致精密半導體零件短路。另一方面，於電子零件容器之表面電阻值大於10¹²Ω/□之情形時，表面產生之靜電難以洩漏，亦對該零件造成不良影響。 The molded article formed by using the conductive resin composite material as described above is suitable for protection if its surface resistance value is 10 ³ to 10 ¹² Ω/□, more preferably 10 ⁶ to 10 ¹² Ω/□. Parts containers for precision semiconductor parts that are not damaged by static electricity, floor materials at the manufacturing site, etc. It is especially suitable for a carrier for IC (integrated circuit) parts such as a carrier tape or a transfer tray for a magnetic head. The reason for this is that an electrostatic short circuit is not caused on the self-charged electronic component, but is slowly removed on the container side. When the resistance value of the container is less than 10 ⁶ Ω/□, the accumulated static electricity rapidly moves to the container to cause a discharge phenomenon, thereby causing a short circuit of the precision semiconductor component. On the other hand, when the surface resistance value of the electronic component container is greater than 10 ¹² Ω/□, the static electricity generated on the surface is hard to leak and adversely affects the component.

具有上述特徵之氣相成長碳纖維結構體並非特別限定者，例如可以如下方式調製。 The vapor-grown carbon fiber structure having the above characteristics is not particularly limited, and can be prepared, for example, in the following manner.

基本上，係以過渡金屬超微粒子為觸媒，將烴等有機化合物以CVD法(chemical vapor deposition，化學氣相沈積法)進行化學熱分解而獲得纖維結構體(以下稱為中間體)，對其進一步進行高溫熱處理。 Basically, a transitional metal ultrafine particle is used as a catalyst to chemically thermally decompose an organic compound such as a hydrocarbon by chemical vapor deposition (chemical vapor deposition) to obtain a fiber structure (hereinafter referred to as an intermediate). It is further subjected to high temperature heat treatment.

作為原料有機化合物，可使用：苯、甲苯、二甲苯等烴，一氧化碳(CO)，乙醇等醇類等。並無特別限定，但為了獲得本發明之纖維結構體，較好的是使用分解溫度不同之至少2種以上之碳化合物作為碳源。再者，本說明書中所述之「至少2種以上之碳化合物」，並非係指必需使用2種以上者作為原料有機化合物者。其係指亦包括如下態樣者：於原料有機化合物使用1種者之情形時，於中間體之合成反應過程中，例如產生如甲苯或二甲苯之加氫脫烷基化(hydrodealkylation)等的反應，而於其後之熱分解反應系統中形成分解溫度不同之2種以上之碳化合物。 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, in order to obtain the fiber structure of the present invention, it is preferred to use at least two or more kinds of carbon compounds having different decomposition temperatures as carbon sources. In addition, the "at least two or more types of carbon compounds" mentioned in this specification does not mean that it is necessary to use two or more types of organic compounds as a raw material. It also includes the following aspects: in the case of using one type of raw material organic compound, during the synthesis reaction of the intermediate, for example, hydrodealkylation such as toluene or xylene is produced. In the subsequent thermal decomposition reaction system, two or more kinds of carbon compounds having different decomposition temperatures are formed.

再者，熱分解反應系統中如上所述使2種以上之碳化合 物存在作為碳源之情形時，各碳化合物之分解溫度不僅根據碳化合物之種類而變動，亦根據原料氣體中之各碳化合物之氣體分壓或莫耳比而變動。因此，可藉由調整原料氣體中之2種以上碳化合物之組成比，而使用比較多之組合來作為碳化合物。 Further, in the thermal decomposition reaction system, two or more kinds of carbons are combined as described above. When the substance is present as a carbon source, the decomposition temperature of each carbon compound varies not only depending on the type of the carbon compound but also depending on the partial pressure of gas or the molar ratio of each carbon compound in the material gas. 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.

例如可自以下化合物中選擇2種以上：甲烷、乙烷、丙烷類、丁烷類、戊烷類、己烷類、庚烷類、環丙烷、環己烷等烷烴或環烷烴，尤其是碳數1~7左右之烷烴；乙烯、丙烯、丁烯類、戊烯類、庚烯類、環戊烯等烯烴或環烯烴，尤其是碳數1~7左右之烯烴；乙炔、丙炔等炔烴，尤其是碳數1~7左右之炔烴；苯、甲苯、苯乙烯、二甲苯、萘、甲基萘、茚、菲等芳香族或雜環芳香族烴，尤其是碳數6~18左右之芳香族或雜環芳香族烴；甲醇、乙醇等醇類，尤其是碳數1~7左右之醇類；此外，一氧化碳、酮類、醚類等。為了將所選擇之2種以上之碳化合物組合使用，調整氣體分壓以便可於所需之熱分解反應溫度區域發揮不同之分解溫度，或者調整特定溫度區域中之滯留時間即可。因此，藉由使2種以上之碳化合物之混合比最佳化，可高效率地製造中間體。 For example, two or more of the following compounds may be selected: an alkane or a cycloalkane such as methane, ethane, propane, butane, pentane, hexane, heptane, cyclopropane or cyclohexane, especially carbon. An alkane of about 1 to 7; an olefin or a cyclic olefin such as ethylene, propylene, butene, pentene, heptene or cyclopentene, especially an olefin having a carbon number of about 1 to 7; an alkyne such as acetylene or propyne Hydrocarbons, especially alkynes with a carbon number of about 1 to 7; aromatic or heterocyclic aromatic hydrocarbons such as benzene, toluene, styrene, xylene, naphthalene, methylnaphthalene, anthracene, phenanthrene, especially carbon 6-18 Aromatic or heterocyclic aromatic hydrocarbons; aromatic alcohols such as methanol and ethanol, especially alcohols having a carbon number of about 1 to 7; and carbon monoxide, ketones, ethers, and the like. In order to use the selected two or more kinds of carbon compounds in combination, the partial pressure of the gas may be adjusted so as to exhibit different decomposition temperatures in the desired thermal decomposition reaction temperature region or to adjust the residence time in the specific temperature region. Therefore, by optimizing the mixing ratio of two or more kinds of carbon compounds, the intermediate can be efficiently produced.

如上所述之2種以上碳化合物之組合中，例如於甲烷與苯之組合中，較好的是甲烷/苯之莫耳比設為1~600，更好的是1.1~200，進而好的是3~100。再者，該值為反應爐之入口處的氣體組成比，例如於使用甲苯作為碳源之一之情形時，考慮到反應爐內甲苯100%分解而以1：1生成甲烷 及苯，另行供給不足部分之甲烷即可。例如於將甲烷/苯之莫耳比設為3之情形時，相對於甲苯1莫耳，添加甲烷2莫耳即可。再者，作為如上所述之對甲苯添加之甲烷，未必僅利用另行準備新鮮之甲烷的方法來使用，亦可將自該反應爐中排出之排氣中所含的未反應之甲烷循環使用。 In the combination of two or more kinds of carbon compounds as described above, for example, in the combination of methane and benzene, it is preferred that the methane/benzene molar ratio is from 1 to 600, more preferably from 1.1 to 200, and further preferably It is 3~100. Further, the value is a gas composition ratio at the inlet of the reaction furnace, for example, when toluene is used as one of the carbon sources, methane is formed at 1:1 in consideration of 100% decomposition of toluene in the reactor. And benzene, the additional part of the methane can be supplied. For example, when the methane/benzene molar ratio is set to 3, methane 2 mole may be added to toluene 1 mole. Further, the methane added as the above-mentioned p-toluene is not necessarily used by a method in which fresh methane is separately prepared, and the unreacted methane contained in the exhaust gas discharged from the reaction furnace may be recycled.

藉由設為上述範圍內之組成比，可獲得具有氣相成長碳纖維以及粒狀部中任一者均充分發達之三維網狀結構的中間體。 By setting the composition ratio within the above range, an intermediate body having a three-dimensional network structure in which the vapor-grown carbon fibers and the granular portions are sufficiently developed can be obtained.

又，未必加以限定，但作為控制纖維外徑之粗細度之要因，可列舉原料中之烴化合物濃度、原料中之烴化合物與觸媒金屬之濃度比率、反應爐內之滯留時間等。 Further, the thickness of the outer diameter of the fiber is determined as a factor of the concentration of the hydrocarbon compound in the raw material, the concentration ratio of the hydrocarbon compound to the catalytic metal in the raw material, and the residence time in the reactor.

因此，為了使氣相成長碳纖維之外徑變粗，例如提高原料中之烴化合物之濃度即可。又，原料中之烴化合物與觸媒金屬之濃度比率係視使外徑變粗之程度，於烴化合物與觸媒金屬之莫耳比中，可稍微提高觸媒金屬之莫耳比。化學氣相沈積法(CVD法)中，為了以觸媒金屬為核而使氣相成長碳纖維成長，較理想的是使所使用之金屬觸媒亦增量。 Therefore, in order to make the outer diameter of the vapor-grown carbon fiber thick, for example, the concentration of the hydrocarbon compound in the raw material may be increased. Further, the concentration ratio of the hydrocarbon compound to the catalytic metal in the raw material is such that the outer diameter becomes thicker, and the molar ratio of the catalytic metal can be slightly increased in the molar ratio of the hydrocarbon compound to the catalytic metal. In the chemical vapor deposition method (CVD method), in order to grow a vapor-grown carbon fiber using a catalytic metal as a core, it is preferable to increase the amount of the metal catalyst to be used.

再者，環境氣體中，可使用氬、氦、氙等惰性氣體或氫。 Further, in the ambient gas, an inert gas such as argon, helium or neon or hydrogen may be used.

又，作為觸媒，係使用鐵、鈷、鉬等過渡金屬或者二茂鐵、醋酸金屬鹽等過渡金屬化合物與硫或者噻吩、硫化鐵等硫化合物的混合物。 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.

中間體之合成可使用通常所進行的烴等之CVD法。使成 為特定調配比之原料之烴及觸媒之混合液蒸發，將氫氣等作為載氣而導入反應爐內，於800~1300℃之溫度下進行熱分解。藉此，合成複數個中間體集合而成之數厘米至數十厘米大小之集合體，上述中間體具有平均纖維外徑為100~300nm之纖維且相互之間藉由如上述觸媒之粒子作為核來成長之粒狀體而結合的疏鬆之三維結構。 As the synthesis of the intermediate, a CVD method such as a hydrocarbon which is usually carried out can be used. Make A specific mixture of a hydrocarbon and a catalyst of a raw material is evaporated, and hydrogen gas 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. Thereby, a plurality of intermediates are assembled into a collection of several centimeters to several tens of centimeters in size, and the intermediate has fibers having an average fiber outer diameter of 100 to 300 nm and is mutually used as particles of the above-mentioned catalyst. A loose three-dimensional structure that combines with the growing granules.

作為包含上述反應爐之製造裝置，並無特別限定，例如可例示具有圖1所示之結構的製造裝置。圖中所示之製造裝置1係使原料蒸發，將氣化之原料與載氣混合，將該原料混合氣體導入至反應爐8之內部，於反應爐8內製造氣相成長碳纖維之集合體者。製造裝置1具備填充有原料之原料槽2、進行原料之搬送以及向反應爐8內之導入的填充有載氣之氣體槽4，該等原料槽2以及氣體槽4經由原料導入管3以及氣體導入管5而分別連接於蒸發器6。進而，蒸發器6係經由原料混合氣體導入管7而連接於反應爐8。而且，製造氣相成長碳纖維之反應爐8內部形成為圓筒狀，於成為其軸心方向之一端的上端，具備使搬送而來之原料混合氣體導入至反應爐8內部的導入噴嘴9。又，於反應爐8之外周部設置有加熱器作為加熱機構11，自反應爐8之外周部加熱反應爐8之內部。而且，於反應爐8之成為軸心方向之他端的下端側，連接有將所製造之氣相成長碳纖維儲備而回收之氣相成長碳纖維回收器12。該氣相成長碳纖維回收器12上連接有排出氣體之氣體排出管13。 The manufacturing apparatus including the above reaction furnace is not particularly limited, and for example, a manufacturing apparatus having the structure shown in Fig. 1 can be exemplified. The manufacturing apparatus 1 shown in the drawing evaporates a raw material, mixes the vaporized raw material with a carrier gas, introduces the raw material mixed gas into the inside of the reaction furnace 8, and produces a collection of vapor-grown carbon fibers in the reaction furnace 8. . The manufacturing apparatus 1 includes a raw material tank 2 filled with a raw material, a raw material, and a gas tank 4 filled with a carrier gas introduced into the reaction furnace 8, and the raw material tank 2 and the gas tank 4 pass through the raw material introduction pipe 3 and the gas. The introduction tube 5 is connected to the evaporator 6, respectively. Further, the evaporator 6 is connected to the reaction furnace 8 via the raw material mixed gas introduction pipe 7. In addition, the inside of the reactor 8 for producing a vapor-grown carbon fiber is formed into a cylindrical shape, and an introduction nozzle 9 for introducing the raw material mixed gas to be conveyed into the inside of the reaction furnace 8 is provided at the upper end which is one end of the axial direction. Further, a heater is provided as a heating means 11 on the outer periphery of the reaction furnace 8, and the inside of the reaction furnace 8 is heated from the outer periphery of the reaction furnace 8. Further, a vapor-phase growth carbon fiber collector 12 that recovers the produced vapor-phase-grown carbon fibers and stores them 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 vapor phase growth carbon fiber recovery unit 12.

成為原料之烴的熱分解反應主要於觸媒粒子或者以其為 核而成長之粒狀體表面上發生。因分解而產生之碳之再結晶化係利用該觸媒粒子或粒狀體而在一定方向上進行者，藉此成長為纖維狀。然而，為了獲得本發明之氣相成長碳纖維結構體，而使如上所述之熱分解速度與成長速度之平衡有意地變化。例如藉由如上所述，使用分解溫度不同之至少2種以上之碳化合物作為碳源，則並非僅於一維方向上使碳物質成長，而是以粒狀體為中心使碳物質三維地成長。當然，此種三維之氣相成長碳纖維之成長並非僅依賴於熱分解速度與成長速度之平衡者，亦受到觸媒粒子之結晶面選擇性、反應爐內之滯留時間、爐內溫度分布等的影響。又，上述熱分解反應與成長速度之平衡不僅受上述碳源之種類的影響，亦受反應溫度以及氣體溫度等的影響。概括而言，若成長速度快於熱分解速度，則碳物質沿著纖維狀而成長，另一方面，若熱分解速度快於成長速度，則碳物質沿著觸媒粒子之周面方向而成長。因此，藉由控制熱分解速度與成長速度之平衡，使其有意地變化，可使碳物質之成長方向不為一定方向而為多方向，從而形成三維結構。再者，較理想的是使觸媒等之組成、反應爐內之滯留時間、反應溫度、以及氣體溫度等最佳化，以便使所生成之中間體中容易形成包含粒狀部與氣相成長碳纖維之三維結構。 The thermal decomposition reaction of hydrocarbons that become raw materials is mainly based on catalyst particles or The nucleus grows on the surface of the granules. The recrystallization of carbon due to decomposition proceeds to a fiber shape by using the catalyst particles or the granules in a predetermined direction. However, in order to obtain the vapor-phase-grown carbon fiber structure of the present invention, the balance between the thermal decomposition rate and the growth rate as described above is intentionally changed. For example, by using at least two or more kinds of carbon compounds having different decomposition temperatures as the carbon source as described above, the carbon material is not grown only in the one-dimensional direction, but the carbon material is grown three-dimensionally around the granular body. . Of course, the growth of such three-dimensional vapor-grown carbon fibers does not depend only on the balance between the thermal decomposition rate and the growth rate, but also on the crystal plane selectivity of the catalyst particles, the residence time in the reactor, and the temperature distribution in the furnace. influences. Further, the balance between the thermal decomposition reaction and the growth rate is affected not only by the type of the carbon source but also by the reaction temperature and the gas temperature. In general, if the growth rate is faster than the thermal decomposition rate, the carbon material grows along the fiber shape. On the other hand, if the thermal decomposition rate is faster than the growth rate, the carbon material grows along the circumferential direction of the catalyst particles. . Therefore, by controlling the balance between the thermal decomposition rate and the growth rate, the intentional change is made, and the growth direction of the carbon material can be multidirectional without being oriented in a certain direction, thereby forming a three-dimensional structure. Further, it is preferable to optimize the composition of the catalyst or the like, the residence time in the reactor, the reaction temperature, and the gas temperature, so that the formed intermediate can be easily formed into a granular portion and a vapor phase. The three-dimensional structure of carbon fiber.

再者，作為高效率地製造中間體之方法，除了以最佳之混合比使用如上所述之分解溫度不同之2種以上碳化合物的方法以外，可列舉使供給至反應爐中之原料氣體在其供 給口附近產生亂流的方法。此處所謂之亂流，係指激烈紊亂之氣流，指呈旋渦狀流動之氣流。 In addition, as a method of efficiently producing an intermediate, in addition to the method of using two or more types of carbon compounds having different decomposition temperatures as described above at an optimum mixing ratio, the raw material gas supplied to the reaction furnace may be mentioned. Its for A method of generating turbulent flow near the mouth. The so-called turbulent flow here refers to a highly turbulent airflow, and refers to a flow of a swirling flow.

反應爐中，原料氣體自該供給口導入反應爐內後，立即藉由原料混合氣體中作為觸媒之過渡金屬化合物之分解而形成金屬觸媒微粒子。此係經過如下階段而達成。即，首先過渡金屬化合物經分解而成為金屬原子，繼而，藉由複數個例如約100原子左右之金屬原子的碰撞而生成團簇(cluster)。於該所生成之團簇的階段，不發揮作為中間體之觸媒的作用，所生成之團簇藉由相互之間碰撞而更進一步集合，成長為約3nm~10nm左右之金屬之結晶性粒子，被用作中間體之製造用金屬觸媒微粒子。 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. This is achieved through the following stages. That is, first, the transition metal compound is decomposed to become a metal atom, and then a cluster is formed by collision of a plurality of metal atoms of, for example, about 100 atoms. At the stage of the cluster formed, the formed cluster does not function as a catalyst for the intermediate, and the generated cluster is further aggregated by collision with each other, and is grown into a crystalline particle of a metal of about 3 nm to 10 nm. It is used as a metal catalyst microparticle for the manufacture of intermediates.

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團簇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，碳化合物之分解反應區域即金屬觸媒表面之面積變大。因此，促進碳化合物之分解，從而充分供給碳物質，以上述集合體之各自之金屬觸媒微粒子為核，氣相成長碳纖維呈放射狀地成長。另一方面，若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維結構之中間體。再者，一般認為上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。一般亦認為於凝集為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為核進行成長而成之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置而形成前驅物之粒狀部。 In the formation of the catalyst, if there is eddy current caused by 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, as the number of collisions per unit time increases, the metal catalyst particles are obtained in a high yield in a short period of time, and the concentration, temperature, and the like are uniformized by the eddy current, thereby obtaining a metal touch having the same particle size. Medium particles. Further, in the process of forming the metal catalyst fine particles, an aggregate of the metal catalyst fine particles in which a large amount of metallic crystal particles are aggregated is formed by the intense collision caused by the eddy current. As a result, the metal catalyst fine particles are rapidly formed, and the area of the decomposition reaction region of the carbon compound, that is, the surface of the metal catalyst becomes large. Therefore, the decomposition of the carbon compound is promoted, and the carbon material is sufficiently supplied, and the metal catalyst fine particles of the aggregate are used as the core, and the vapor-grown carbon fibers grow radially. On the other hand, if a part of the carbon compound is thermally decomposed faster than carbon as described above At the growth rate of the substance, the carbon material grows in the circumferential direction of the catalyst particles, and a granular portion is formed around the aggregate to efficiently form an intermediate body having a desired three-dimensional structure. Further, it is considered that the aggregate of the above-mentioned metal catalyst fine particles also includes a part of the catalyst fine particles whose activity is lower than that of the other catalyst fine particles or which is inactive during the reaction. It is also considered to be a non-fibrous or extremely short fibrous carbon material which grows on the surface of the above-mentioned catalyst fine particles before agglomerating into an aggregate or which is grown by using the above-mentioned catalyst fine particles as a core after forming an aggregate. A granular portion that forms a precursor at a peripheral position of the aggregate.

因此，粒狀部包含複數個氣相成長碳纖維之端部、與僅於周面方向使碳物質成長的金屬觸媒微粒子，並且，較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。在如此狀態下使碳物質之成長進一步繼續，與後述之退火處理互起作用，從而在粒狀部集合˙集積之複數個氣相成長碳纖維之端部或複數個球狀結構物鄰接者形成˙共有連續的石墨片狀層。藉此，形成以複數個粒狀部與氣相成長碳纖維牢固結合之三維網狀之氣相成長碳纖維結構體。 Therefore, the granular portion includes the end portions of the plurality of vapor-grown carbon fibers, and the metal catalyst particles which grow the carbon material only in the circumferential direction, and the aggregated ̇ accumulation pattern of the plurality of spherical structures is formed. Not just a sphere. In this state, the growth of the carbonaceous material is further continued, and the annealing treatment, which will be described later, acts to form an end portion of the plurality of vapor-phase-growth carbon fibers or a plurality of spherical structures adjacent to the aggregate of the particulate portion. There are a continuous layer of graphite flakes. Thereby, a three-dimensional network vapor-grown carbon fiber structure in which a plurality of granular portions are strongly bonded to the vapor-grown carbon fibers is formed.

於反應爐之原料氣體供給口附近，作為所投入之原料氣體之溫度，較好的是350~450℃，作為使原料氣體之氣流產生亂流之具體方法，並無特別限定。例如可採用：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。作為上述碰撞部之形狀，並無任何限 定，若為由於以碰撞部為起點所產生之渦流而於反應爐內形成充分之亂流者即可。例如可將各種形狀之隔板、槳、錐管、傘狀體等單獨或者組合複數個而採用配置1個或複數個之形態。 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 350 to 450 ° C, and is not particularly limited as a specific method for causing a turbulent flow of the raw material gas. For example, a method in which a raw material gas is introduced into the reaction furnace by a swirling flow, or a method in which a collision portion or the like is provided at a position that can interfere with the flow of the raw material gas which is discharged from the raw material gas supply port into the reaction furnace can be employed. As the shape of the above collision portion, there is no limit. It is sufficient if a turbulent flow is formed in the reaction furnace due to the eddy current generated from the collision portion. For example, a separator, a paddle, a tapered tube, an umbrella, or the like of various shapes may be used alone or in combination, and one or a plurality of them may be arranged.

於圖1所例示之製造裝置1中，作為上述碰撞部之例子，於導入噴嘴9周圍設有整流˙緩衝板10。整流˙緩衝板係配置於導入噴嘴9附近，作為阻礙原料混合氣體之流通的碰撞之起點而發揮作用之障礙物，可藉由該障礙物與原料混合氣體碰撞而產生渦流，使溫度分布與濃度分布均勻化。整流˙緩衝板之形狀並無任何限定，若為以整流˙緩衝板為起點所產生之渦流不消失，且逐次形成至反應爐8之下端側的形狀即可。 In the manufacturing apparatus 1 illustrated in Fig. 1, as the example of the collision portion, a rectifying buffer plate 10 is provided around the introduction nozzle 9. The rectifying buffer plate is disposed in the vicinity of the introduction nozzle 9 and acts as an obstacle that hinders the collision of the flow of the raw material mixed gas. The obstacle can collide with the raw material mixed gas to generate eddy current, and the temperature distribution and concentration can be made. The distribution is uniform. The shape of the rectifying buffer plate is not limited, and the eddy current generated from the rectifying buffer plate does not disappear, and is formed in a shape successively to the lower end side of the reaction furnace 8.

將觸媒以及烴之混合氣體於設定為800~1300℃之範圍的溫度下加熱生成而獲得之中間體，具有由碳原子而成之貼片狀薄片貼附合起的結構。該中間體若進行拉曼光譜分析，則D譜帶非常大，且缺陷多。又，含有未反應原料、非纖維狀碳化物、焦油成分以及觸媒金屬。 An intermediate obtained by heating a mixed gas of a catalyst and a hydrocarbon at a temperature set to a range of 800 to 1300 ° C, and having a structure in which a patch-like sheet made of carbon atoms is attached. If the intermediate is subjected to Raman spectroscopy, the D band is very large and has many defects. Further, it contains an unreacted raw material, a non-fibrous carbide, a tar component, and a catalytic metal.

因此，為了自如上所述之中間體中除去該等殘留物而獲得缺陷少之所需碳纖維結構體，利用適當方法於2400~3000℃之高溫下進行熱處理即可。 Therefore, in order to obtain the desired carbon fiber structure having few defects from the intermediates as described above, heat treatment may be carried out at a high temperature of 2400 to 3000 ° C by an appropriate method.

例如，藉由將該中間體於800~1200℃下加熱而除去未反應原料及焦油成分等揮發成分後，於2400~3000℃之高溫下進行退火處理，來調製所需之結構體，同時使纖維中所含之觸媒金屬蒸發而除去。再者，此時為了保護物質結 構，亦可於惰性氣體環境中添加還原氣體或微量之一氧化碳氣體。 For example, the intermediate is removed at 800 to 1200 ° C to remove volatile components such as unreacted raw materials and tar components, and then annealed at a high temperature of 2400 to 3000 ° C to prepare a desired structure. The catalyst metal contained in the fiber is removed by evaporation. Furthermore, at this time, in order to protect the material knot It is also possible to add a reducing gas or a trace of one carbon monoxide gas in an inert gas atmosphere.

若將上述中間體於2400~3000℃之範圍之溫度下進行退火處理，則由碳原子而成之貼片狀薄片分別結合而形成複數個石墨片狀層，從而獲得所需之氣相成長碳纖維。 When the intermediate is annealed at a temperature in the range of 2400 to 3000 ° C, the patch-like sheets made of carbon atoms are combined to form a plurality of graphite sheet layers, thereby obtaining a desired vapor-grown carbon fiber. .

再者，具有上述平均纖維外徑以及纖維外徑分布之標準偏差值的氣相成長碳纖維，於氣相成長碳纖維之製造方法中，若為批量式，則可為在1次製造反應中獲得者。若為連續反應，則可為將獲得適當之製造量的1連續期間作為1次而獲得之氣相成長碳纖維，或者亦可為如此獲得之氣相成長碳纖維之複數次量之混合物。 Further, the vapor-grown carbon fiber having the above-mentioned average fiber outer diameter and the standard deviation value of the fiber outer diameter distribution may be a one-time production reaction in the production method of the vapor-phase-grown carbon fiber. . In the case of a continuous reaction, it may be a vapor-grown carbon fiber obtained by obtaining a continuous period of 1 for a suitable production amount, or may be a mixture of a plurality of times of the vapor-grown carbon fibers thus obtained.

本發明中，導電性樹脂複合材料中之聚碳酸酯樹脂與氣相成長碳纖維之含量較好的是，相對於聚碳酸酯樹脂100質量份，氣相成長碳纖維為1~11.2質量份，更好的是3~7.7質量份。若含量為如上所述，則可實現良好之導電性、與成形性相關之斷裂伸長率之改善以及氣相成長碳纖維自樹脂複合材料之脫落之減少。若氣相成長碳纖維之含量小於1質量份，則無法獲得目標之導電性，因此複合材料表面所產生之靜電難以洩漏，若大於11.2，則有不僅導電性變得過高，並且引起母材聚碳酸酯樹脂之物性下降之虞。 In the present invention, the content of the polycarbonate resin and the vapor-grown carbon fiber in the conductive resin composite material is preferably from 1 to 11.2 parts by mass, more preferably from 100 parts by mass of the polycarbonate resin. It is 3 to 7.7 parts by mass. When the content is as described above, it is possible to achieve good electrical conductivity, improvement in elongation at break associated with formability, and reduction in drop-off of vapor-grown carbon fibers from the resin composite. When the content of the vapor-grown carbon fiber is less than 1 part by mass, the target conductivity cannot be obtained, so that static electricity generated on the surface of the composite material is hard to leak, and if it is more than 11.2, not only the conductivity becomes too high, but also the base material is aggregated. The physical properties of the carbonate resin are degraded.

又，上述氣相成長碳纖維自導電性樹脂複合材料之脫落性為，將該複合材料(50×90×3mm)浸漬於超純水2000ml中，施加47kHz之超音波60秒後，自該複合材料之表面脫落的粒徑為0.5μm以上之顆粒之數量於該複合材料之每單 位表面積中為5000個/cm²以下，較好的是2500個/cm²以下。 Further, the detachment property of the vapor-grown carbon fiber from the conductive resin composite material was such that the composite material (50 × 90 × 3 mm) was immersed in 2000 ml of ultrapure water, and ultrasonic waves of 47 kHz were applied for 60 seconds, and then the composite material was used. The number of particles having a particle diameter of 0.5 μm or more which is detached from the surface is 5,000 / cm ² or less per unit surface area of the composite material, preferably 2,500 / cm ² or less.

又，關於向聚碳酸酯樹脂中添加混合氣相成長碳纖維來製造導電性樹脂複合材料之方法，該製造方法並非特別限定者。然而，由於對於氣相成長碳纖維之分散而言必需具有優異之混練性能，故而較好的是使用雙軸擠出機將聚碳酸酯樹脂與氣相成長碳纖維熔融混練。又，本發明之導電性樹脂複合材料自其特性而言，具有可使用熱負荷大之大型雙軸擠出機的優點。 In addition, a method of producing a conductive resin composite by adding a vapor-grown carbon fiber to a polycarbonate resin is not particularly limited. However, since it is necessary to have excellent kneading performance for dispersion of the vapor-grown carbon fibers, it is preferred to melt-mix the polycarbonate resin and the vapor-grown carbon fibers using a twin-screw extruder. Further, the conductive resin composite material of the present invention has an advantage that a large-sized twin-screw extruder having a large heat load can be used from its characteristics.

作為雙軸擠出機之代表例子，可列舉ZSK(商品名，Werner & Pfleiderer公司製造)。作為同樣類型之具體例，可列舉TEX(商品名，(股)日本製鋼所製造)、TEM(商品名，東芝機械(股)製造)、KTX(商品名，(股)神戶製鋼所製造)等。此外，亦可列舉FCM(商品名，Farrel公司製造)、Ko-Kneader(商品名，Buss公司製造)、以及DSM(商品名，Krauss-Maffei公司製造)等熔融混練機作為具體例。上述之中更好的是以ZSK為代表之類型。該ZSK類型之雙軸擠出機中，其螺桿係完全嚙合型，螺桿係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(或者與其相當之混練用區段)者。 As a representative example of the twin-screw extruder, ZSK (trade name, manufactured by Werner & Pfleiderer Co., Ltd.) can be cited. Specific examples of the same type include TEX (trade name, manufactured by Nippon Steel Co., Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (trade name, manufactured by Kobe Steel Co., Ltd.), and the like. . Further, a melt kneading machine such as FCM (trade name, manufactured by Farrel Co., Ltd.), Ko-Kneader (trade name, manufactured by Buss Co., Ltd.), and DSM (trade name, manufactured by Krauss-Maffei Co., Ltd.) may be mentioned as a specific example. More preferably, the above is a type represented by ZSK. In the ZSK type twin-screw extruder, the screw is completely meshed, and the screw system includes various screw segments having different lengths and pitches, and various kneading discs having different widths (or a kneading section equivalent thereto).

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搬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，容易由於熱劣化而產生母材樹脂之分解。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。 A better aspect of the twin screw extruder is as follows. One, two, or three screw screws may be used for the screw shape, and it is particularly preferable to use two screw screws having a wide range of application of the molten resin or the shearing kneading ability. The ratio of the length (L) to the diameter (D) of the screw of the twin-screw extruder is higher than that of the diameter (L/D) The good is 20~50, and the better is 28~42. In the case where the L/D is large, it is easy to achieve homogenization dispersion. On the other hand, when it is too large, decomposition of the base material resin is likely to occur due to thermal deterioration. It is necessary to have one or more kneading regions composed of a kneading disc segment (or a kneading section equivalent thereto) for improving kneading, preferably having 1 to 3 places.

作為擠出機，可較好地使用具有可將原料中之水分、或自熔融混練樹脂產生之揮發氣體脫氣之排氣口者。排氣口較好的是設置用以將產生之水分或揮發氣體高效率地排出至擠出機外部的真空泵。又，為了提高氣相成長碳纖維之分散性，或者儘可能除去樹脂複合材料中之雜質，可添加水、有機溶劑、以及超臨界流體等。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。作為該篩網，可列舉金屬絲網、換網器、燒結金屬板(圓盤濾片等)等。 As the extruder, those having an exhaust port capable of deaerating the moisture in the raw material or the volatile gas generated from the melt-kneading resin can be preferably used. Preferably, the exhaust port is provided with a vacuum pump for efficiently discharging the generated moisture or volatile gas to the outside of the extruder. Further, in order to increase the dispersibility of the vapor-grown carbon fibers or to remove impurities in the resin composite as much as possible, water, an organic solvent, a supercritical fluid or the like 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 screen changer, a sintered metal plate (such as a disk filter), and the like.

將氣相成長碳纖維向擠出機供給之方法並無特別限定，可代表性地例示以下方法。(i)將氣相成長碳纖維與聚碳酸酯樹脂獨立地供給至擠出機中之方法。(ii)將氣相成長碳纖維與聚碳酸酯樹脂粉末使用高速混合機等混合機進行預備混合後，供給至擠出機中之方法。(iii)將氣相成長碳纖維與聚碳酸酯樹脂預先熔融混練而使其成為主要顆粒，將其作為氣相成長碳纖維源予以供給之方法。 The method of supplying the vapor-grown carbon fiber to the extruder is not particularly limited, and the following method can be typically exemplified. (i) A method of separately supplying a vapor-grown carbon fiber and a polycarbonate resin to an extruder. (ii) A method in which a vapor-grown carbon fiber and a polycarbonate resin powder are premixed by using a mixer such as a high-speed mixer, and then supplied to an extruder. (iii) A method in which a vapor-grown carbon fiber and a polycarbonate resin are melt-kneaded in advance to be a main particle, and this is supplied as a vapor-grown carbon fiber source.

再者，於使用平均纖維外徑不同之氣相成長碳纖維之情形時，可於上述(i)步驟之前將氣相成長碳纖維相互混合，而且亦可於上述(i)~(iii)之步驟時將氣相成長碳纖維相互 混合。 Further, in the case of using a vapor-grown carbon fiber having an average outer diameter of the fiber, the vapor-grown carbon fibers may be mixed with each other before the step (i), and may also be in the steps (i) to (iii) above. Vapor-grown carbon fiber mixing.

又，較好的是，將寬度為50mm、長度為90mm、厚度為3mm之上述導電性樹脂複合材料浸漬於超純水2000mL中，施加47kHz之超音波60秒時，自表面脫落的粒徑為0.5μm以上之脫落物之數量於每單位表面積中為5000個/cm²以下。若脫落物之數量為5000個/cm²以下，則例如於本發明在半導體領域中使用之情形時，可抑制由脫落物引起的半導體製品之故障˙損壞。 Moreover, it is preferable that the conductive resin composite material having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm is immersed in 2000 mL of ultrapure water, and when ultrasonic waves of 47 kHz are applied for 60 seconds, the particle diameter falling off from the surface is The amount of the detached material of 0.5 μm or more is 5,000/cm ² or less per unit surface area. When the amount of the exfoliated material is 5,000 / cm ² or less, for example, when the present invention is used in the field of semiconductors, failure or damage of the semiconductor article caused by the detachment can be suppressed.

本發明者目前認為最佳的本發明之形態係將實現上述各用途中之較佳應用之範圍概括而成者，例如其代表例記載於下述實施例中。當然本發明並非限定於該等形態者。 The present inventors have now considered that the preferred embodiment of the present invention is intended to achieve a general range of applications for the above-described respective applications. For example, representative examples thereof are described in the following examples. Of course, the invention is not limited to these forms.

實施例 Example [氣相成長碳纖維結構體(粗徑品)之調製] [Preparation of vapor-phase growth carbon fiber structure (thick diameter product)]

使用圖1所示之製造裝置，於下述表1所示之條件下獲得氣相成長碳纖維結構體之中間體後，於氬氣中、900℃下進行煅燒，將作為雜質而含有之焦油等之烴分離，進行純化。繼而，將該中間體於氬氣中進行2600℃之高溫熱處理(退火處理)，進而利用氣流粉碎機進行粉碎。藉此，獲得氣相成長碳纖維之平均纖維外徑為117nm，形成三維網狀結構體之氣相成長碳纖維結構體(圖2以及圖3)。 Using the production apparatus shown in Fig. 1, an intermediate of a vapor-phase-grown carbon fiber structure was obtained under the conditions shown in Table 1 below, and then calcined in an argon atmosphere at 900 ° C to contain tar as an impurity. The hydrocarbons are separated and purified. Then, this intermediate was subjected to a high-temperature heat treatment (annealing treatment) at 2600 ° C in argon gas, and further pulverized by a jet mill. Thereby, the vapor-grown carbon fiber structure in which the average fiber outer diameter of the vapor-grown carbon fiber was 117 nm and the three-dimensional network structure was formed (FIG. 2 and FIG. 3) was obtained.

[氣相成長碳纖維結構體(細徑品)之調製] [Preparation of vapor-phase growth carbon fiber structure (small diameter product)]

使用圖1所示之製造裝置，於下述表1所示之條件下獲得氣相成長碳纖維結構體之中間體後，於氬氣中、900℃下進行煅燒，將作為雜質而含有之焦油等之烴分離，進行純 化。繼而，將該中間體於氬氣中進行2600℃之高溫熱處理(退火處理)，進而利用氣流粉碎機進行粉碎。藉此，獲得氣相成長碳纖維之平均纖維外徑為58nm，形成三維網狀結構體之氣相成長碳纖維結構體。 Using the production apparatus shown in Fig. 1, an intermediate of a vapor-phase-grown carbon fiber structure was obtained under the conditions shown in Table 1 below, and then calcined in an argon atmosphere at 900 ° C to contain tar as an impurity. Separation of hydrocarbons, pure Chemical. Then, this intermediate was subjected to a high-temperature heat treatment (annealing treatment) at 2600 ° C in argon gas, and further pulverized by a jet mill. Thereby, a vapor-grown carbon fiber structure in which the average fiber outer diameter of the vapor-grown carbon fibers was 58 nm and the three-dimensional network structure was formed was obtained.

[實施例1] [Example 1]

對於聚碳酸酯樹脂(Lexan 141R(商品名，SABIC Innovative Plastics公司製造))100質量份，添加如上所述而獲得之氣相成長碳纖維結構體(粗徑品)6.38質量份，混合均勻。使用螺桿直徑為30mm之排氣式雙軸擠出機TEX-30XSST(商品名，(股)日本製鋼所製造)，將該混合物供給至最後部之第1投入口。該擠出機於第1供給口至第2供給口之間具有捏合盤之混練區域，且於其正後方設有開放的排氣口。相對於螺桿直徑(D)，排氣口之長度約為2D。該排氣口之後設置有側面進料機，側面進料機後進而設置有捏合盤之混練區域以及與其相連之排氣口。該部分之排氣口之長度約為1.5D，在該部分中使用真空泵而設為約3 kPa之減壓度。擠出係於料筒溫度為300℃(自螺桿根部之滾筒大致均等地上升至模頭位置)、螺桿轉速為180rpm、以及每小時之吐出量為20kg的條件下進行。將擠出之股線在水浴中冷卻後，利用造粒機切斷而使其成為顆粒。將所獲得之顆粒於120℃下乾燥5小時，再利用熱風循環式乾燥機於100℃下乾燥24小時後，使用射出成形機(東芝機械IS55FPB)，於料筒溫度為300℃、模具溫度為80℃、射速為20mm/sec、以及成形週期約為60秒之條件下，製作評價用試驗片。 To 100 parts by mass of a polycarbonate resin (trade name, manufactured by SABIC Innovative Plastics Co., Ltd.), 6.38 parts by mass of a vapor-phase-growth carbon fiber structure (thick diameter product) obtained as described above was added and uniformly mixed. A ventilated twin-screw extruder TEX-30XSST (trade name, manufactured by Nippon Steel Co., Ltd.) having a screw diameter of 30 mm was used, and the mixture was supplied to the first input port of the last portion. The extruder has a kneading zone of a kneading disc between the first supply port and the second supply port, and an open exhaust port is provided directly behind the nozzle. The length of the exhaust port is about 2D with respect to the screw diameter (D). A side feeder is disposed behind the exhaust port, and a side kneading machine is further provided with a kneading zone of the kneading disc and an exhaust port connected thereto. The length of the exhaust port of this part is about 1.5D, and it is set to about 3 using a vacuum pump in this part. The degree of decompression of kPa. The extrusion was carried out under the conditions that the cylinder temperature was 300 ° C (the drum from the screw root portion was raised substantially equally to the die position), the screw rotation speed was 180 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 granulated. The obtained pellets were dried at 120 ° C for 5 hours, and then dried at 100 ° C for 24 hours using a hot air circulation dryer, and then an injection molding machine (Toshiba Machine IS55FPB) was used, and the cylinder temperature was 300 ° C, and the mold temperature was A test piece for evaluation was produced under conditions of 80 ° C, a rate of incidence of 20 mm/sec, and a molding cycle of about 60 seconds.

[實施例2] [Embodiment 2]

除了將氣相成長碳纖維結構體(粗徑品)之添加量設為7.53質量份以外，以與實施例1相同之方法製作評價用試驗片。 A test piece for evaluation was produced in the same manner as in Example 1 except that the amount of addition of the vapor-grown carbon fiber structure (thick diameter) was 7.53 parts by mass.

[實施例3] [Example 3]

將氣相成長碳纖維結構體(粗徑品)以及氣相成長碳纖維結構體(細徑品)以5：1之質量比加入密閉槽中，攪拌2小時以上，獲得氣相成長碳纖維結構體之混合物。該混合物之氣相成長碳纖維之平均纖維外徑為102nm。除了將該混合物之添加量設為6.38質量份，來代替氣相成長碳纖維結構體(粗徑品)以外，以與實施例1相同之方法製作評價用試驗片。 The vapor-grown carbon fiber structure (thick diameter) and the vapor-grown carbon fiber structure (thin diameter) are added to the closed tank at a mass ratio of 5:1, and stirred for 2 hours or more to obtain a mixture of vapor-grown carbon fiber structures. . The vapor-grown carbon fibers of the mixture had an average fiber outer diameter of 102 nm. A test piece for evaluation was produced in the same manner as in Example 1 except that the amount of the mixture was changed to 6.38 parts by mass in place of the vapor-grown carbon fiber structure (large diameter product).

[比較例1] [Comparative Example 1]

除了將氣相成長碳纖維結構體(細徑品)之添加量設為4.17質量份，來代替氣相成長碳纖維結構體(粗徑品)以 外，以與實施例1相同之方法製作評價用試驗片。 In place of the vapor-grown carbon fiber structure (thick diameter), the addition amount of the vapor-grown carbon fiber structure (thin diameter) is set to 4.17 parts by mass. A test piece for evaluation was produced in the same manner as in Example 1.

[比較例2] [Comparative Example 2]

除了將氣相成長碳纖維結構體(細徑品)之添加量設為6.38質量份，來代替氣相成長碳纖維結構體(粗徑品)以外，以與實施例1相同之方法製作評價用試驗片。 A test piece for evaluation was produced in the same manner as in Example 1 except that the gas phase-growth carbon fiber structure (thick diameter product) was added in an amount of 6.38 parts by mass. .

評價用試驗片之物性係根據以下方法進行測定。 The physical properties of the test piece for evaluation were measured by the following methods.

(1)表面電阻率 (1) Surface resistivity

參照JIS K 7194(利用導電性塑膠之4探針法的電阻率試驗方法)，測定位置以及測定方法係依據其，使用Loresta GP(商品名，MCP-T600型，三菱化學(股)製造)、Hiresta UP(商品名，MCP-HT450型，三菱化學(股)製造)，測定射出成形之試驗片(50×90×3mm)之表面電阻並示於表2中。 The measurement position and the measurement method are based on JIS K 7194 (the resistivity test method using the 4-probe method of the conductive plastic), and the Loresta GP (trade name, MCP-T600 type, manufactured by Mitsubishi Chemical Corporation) is used. Hiresta UP (trade name, model MCP-HT450, manufactured by Mitsubishi Chemical Corporation), and the surface resistance of the injection-molded test piece (50 × 90 × 3 mm) were measured and shown in Table 2.

(2)斷裂伸長率 (2) Elongation at break

依據ISO527-1(通則)以及527-2(模具成型、擠出成型以及注模塑膠之試驗條件)，測定拉伸斷裂伸長率。射出成型之試驗片之形狀以及尺寸為ISO527-2之試驗片1A形。試驗裝置係使用萬能材料試驗機(Intesco 2005-5型)，試驗速度為50mm/min，夾頭間距離為115mm，於23℃、50% RH之試驗環境下進行。算出以與上述同樣之方式成型以及測定的5片試驗片之斷裂伸長率值之平均值，並示於表2中。 The tensile elongation at break was measured in accordance with ISO 527-1 (General Rules) and 527-2 (Test conditions for mold forming, extrusion molding, and injection molding of plastics). The shape of the test piece for injection molding and the test piece 1A of the size of ISO527-2 were used. The test apparatus was a universal material testing machine (Intesco 2005-5 type), the test speed was 50 mm/min, and the distance between the chucks was 115 mm, and it was carried out under the test environment of 23 ° C and 50% RH. The average value of the elongation at break values of the five test pieces molded and measured in the same manner as above was calculated and shown in Table 2.

(3)脫落性 (3) shedding

於以超純水清洗之3000mL玻璃燒杯中，注入超純水2000mL，浸漬1片射出成形之試驗片(50×90×3mm)。其後，利用5210E-DTH(47kHz/140W)(商品名，BRANSON 公司製造)施加1分鐘超音波。然後，利用液中微粒子計測器HIAC ROYCO SYSTEM8011(商品名，HACH ULTRA ANALYTICS公司製造)來吸引所抽出之超純水，測定塵埃粒徑為0.5μm以上之發塵量，並示於表2中。 In a 3000 mL glass beaker washed with ultrapure water, 2000 mL of ultrapure water was poured, and one piece of injection-molded test piece (50 × 90 × 3 mm) was immersed. Thereafter, use 5210E-DTH (47kHz/140W) (trade name, BRANSON) The company manufactures) applying a 1 minute ultrasonic wave. Then, the extracted ultrapure water was sucked by a liquid microparticle measuring instrument HIAC ROYCO SYSTEM 8011 (trade name, manufactured by HACH ULTRA ANALYTICS Co., Ltd.), and the amount of dust having a dust particle diameter of 0.5 μm or more was measured and shown in Table 2.

如表2所示之結果所述，使用氣相成長碳纖維之平均纖維外徑超過100nm之氣相成長碳纖維的粗徑品之實施例1~2中，表現出充分之表面電阻值以及較低之脫落性。在 斷裂伸長率方面，相對於細徑品之比較例1~2小於30%，粗徑品之實施例1~2則高於30%。又，藉由將氣相成長碳纖維之平均纖維外徑較粗之氣相成長碳纖維結構體與較細之氣相成長碳纖維結構體混合而增大標準偏差值的混合品之實施例3中，同樣表現出充分之表面電阻值、以及與粗徑品之實施例1~2同樣較低的脫落性。尤其，斷裂伸長率為60%，得到明顯改善。 As shown in the results shown in Table 2, in Examples 1 to 2 in which the large-diameter products of the vapor-grown carbon fibers having an average fiber outer diameter of more than 100 nm of the vapor-grown carbon fibers were used, sufficient surface resistance values and lower values were exhibited. Shedding. in In terms of elongation at break, Comparative Examples 1 to 2 were less than 30% with respect to the small diameter products, and Examples 1 to 2 of the large diameter products were higher than 30%. In the third embodiment, the mixture of the vapor-phase-grown carbon fiber structure in which the average fiber outer diameter of the vapor-grown carbon fiber is mixed with the fine vapor-grown carbon fiber structure is increased, and the standard deviation value is increased. It exhibited a sufficient surface resistance value and the same low peeling property as in Examples 1 and 2 of the large diameter product. In particular, the elongation at break was 60%, which was remarkably improved.

產業上之可利用性 Industrial availability

本發明之導電性樹脂複合材料在OA(office automation，辦公室自動化)機器領域、電氣電子設備領域等各種工業用途中極為有用，其所發揮之工業效果極大。 The conductive resin composite material of the present invention is extremely useful in various industrial applications such as OA (office automation) equipment and electric and electronic equipment, and has an industrial effect.

又，本發明之導電性樹脂複合材料係藉由將上述所說明之氣相成長碳纖維調配於聚碳酸酯樹脂中，而具有優異之導電性、經改善之斷裂伸長率以及氣相成長碳纖維難以脫落之特性者。藉由該特性，導電性樹脂複合材料應對廣泛之成形條件，且其成形之抗裂性優異，因此可提供可應用於廣泛用途中之導電性材料。作為該用途，例如可例示：個人電腦、筆記型電腦、遊戲機(家用遊戲機、業務用遊戲機、彈珠台(pachinko)以及吃角子老虎(slot machine)等)、顯示裝置(LCD(liquid crystal display，液晶顯示器)、有機EL(electroluminescence，電致發光)、電子紙、電漿顯示器、以及投影儀等)、輸電零件(以感應線圈式輸電裝置之外罩為代表)。又，作為該用途，例如可例示印表機、影印機、掃描機以及傳真機(包括該等之複合機)。 進而，作為該用途，可例示：VTR(video tape recorder，磁帶錄影機)相機、光學膜式相機、數位靜態相機、相機用透鏡單元、防盜裝置、以及行動電話等精密機器。尤其，本發明之樹脂組合物適宜用於相機鏡筒、數位相機等數位圖像資訊處理裝置之框體、外殼、以及框。 Further, the conductive resin composite material of the present invention has excellent conductivity, improved elongation at break, and vapor-phase growth of carbon fibers which are difficult to fall off by blending the above-described vapor-phase-growth carbon fibers in a polycarbonate resin. The characteristics of the person. According to this characteristic, the conductive resin composite material can satisfy 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. Examples of the use include a personal computer, a notebook computer, a game machine (a home game machine, a business game machine, a pachinko, and a slot machine), and a display device (LCD (liquid)). Crystal display, liquid crystal display, organic EL (electroluminescence), electronic paper, plasma display, and projector, etc., transmission parts (represented by the cover of the induction coil type power transmission device). Moreover, as such a use, for example, a printer, a photocopier, a scanner, and a facsimile machine (including these multifunction machines) can be exemplified. Further, as such a use, a VTR (video tape recorder) camera, an optical film camera, a digital still camera, a camera lens unit, an antitheft device, and a precision machine such as a mobile phone can be exemplified. In particular, the resin composition of the present invention is suitably used for a frame, a casing, and a frame of a digital image information processing device such as a camera barrel or a digital camera.

此外，本發明之導電性樹脂複合材料亦適用於：按摩機或高氧治療器等醫療機器；錄像機(所謂DVD錄影機等)、視聽機器、以及電子樂器等家電製品；彈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用機器人等之零件。 Further, the conductive resin composite material of the present invention is also suitable for use in medical devices such as massage machines and hyperoxic therapeutic devices; home appliances such as video recorders (so-called DVD recorders), audio-visual equipment, and electronic musical instruments; pinball tables or horns Game devices such as tigers; and parts such as home robots equipped with precision sensors.

另外，本發明之導電性樹脂複合材料可用於：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、匣式磁碟、光學卡、IC記憶卡、連接器、電纜耦合器、電子零件之搬送用容器(IC卡槽箱、矽晶圓容器、玻璃基板收納容器、磁頭托盤、以及載帶等)、抗靜電用或者除靜電零件(電子照片感光裝置之帶電輥等)、以及各種機構零件(包括齒輪、轉盤、轉子、以及螺絲等。包括微型機器用機構零件)。 In addition, 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, cymbal disks, optical cards, IC memory cards, 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-eliminating parts (electrical roller for electronic photosensitive devices, etc.) ), as well as various mechanical parts (including gears, turntables, rotors, and screws, etc., including mechanical parts for micromachines).

1‧‧‧氣相成長碳纖維之製造裝置 1‧‧‧Mechanical device for vapor-grown carbon fiber

2‧‧‧原料槽 2‧‧‧Material tank

3‧‧‧原料導入管 3‧‧‧Material introduction tube

4‧‧‧氣體槽 4‧‧‧ gas trough

5‧‧‧氣體導入管 5‧‧‧ gas introduction tube

6‧‧‧蒸發器 6‧‧‧Evaporator

7‧‧‧原料混合氣體導入管 7‧‧‧Material mixed gas introduction pipe

8‧‧‧反應爐 8‧‧‧Reaction furnace

9‧‧‧導入噴嘴 9‧‧‧Introduction nozzle

10‧‧‧整流˙緩衝板 10‧‧‧Rectifier ̇ Buffer Board

11‧‧‧加熱機構 11‧‧‧heating mechanism

12‧‧‧氣相成長碳纖維回收器 12‧‧‧Vapor Growth Carbon Fiber Recycler

13‧‧‧氣體排出管 13‧‧‧ gas discharge pipe

14‧‧‧原料混合氣體導入口 14‧‧‧ Raw material mixed gas inlet

15‧‧‧冷卻氣體導入口 15‧‧‧Cooling gas inlet

16‧‧‧冷卻氣體出口 16‧‧‧Cooling gas outlet

20‧‧‧金屬觸媒粒子生成區域 20‧‧‧Metal catalyst particle generation area

30‧‧‧氣相成長碳纖維製造區域 30‧‧‧Vapor-producing carbon fiber manufacturing area

圖1係示意性表示本實施形態之氣相成長碳纖維製造裝置之結構的結構圖；圖2係實施例中製造之氣相成長碳纖維結構體(粗徑品)之5000倍SEM(scanning electron microscope，掃描式電子顯微鏡)照片； 圖3係實施例中製造之氣相成長碳纖維結構體(粗徑品)之粒狀部之50000倍TEM(transmission electron microscope，穿透式電子顯微鏡)照片。 Fig. 1 is a structural view schematically showing the structure of a vapor-grown carbon fiber producing apparatus of the present embodiment; and Fig. 2 is a 5000 times SEM (scanning electron microscope) of a vapor-grown carbon fiber structure (thick diameter) manufactured in the embodiment. Scanning electron microscope) photo; Fig. 3 is a 50,000-times TEM (transmission electron microscope) photograph of a granular portion of a vapor-grown carbon fiber structure (large diameter product) produced in the examples.

Claims (8)

一種導電性樹脂複合材料，其特徵在於：其係含有聚碳酸酯樹脂以及氣相成長碳纖維者，該氣相成長碳纖維之平均纖維外徑為超過100nm且150nm以下，該聚碳酸酯樹脂與該氣相成長碳纖維之混合比係相對於聚碳酸酯樹脂100質量份，該氣相成長碳纖維為1~11.2質量份，並且其斷裂伸長率為30%以上，其中氣相成長碳纖維自上述導電性複合材料上之脫落性為，將該複合材料(50×90×3mm)浸漬於超純水2000mL中，施加47kHz之超音波60秒後，自該複合材料之表面脫落的粒徑為0.5μm以上之顆粒之數量於該複合材料之每單位表面積中為5000個/cm²以下。 A conductive resin composite material comprising a polycarbonate resin and a vapor-grown carbon fiber, wherein the vapor-grown carbon fiber has an average fiber outer diameter of more than 100 nm and 150 nm or less, and the polycarbonate resin and the gas The mixing ratio of the phase-growth carbon fibers is 1 to 11.2 parts by mass relative to 100 parts by mass of the polycarbonate resin, and the elongation at break is 30% or more, wherein the vapor-grown carbon fibers are from the above-mentioned conductive composite material. The detachment property is such that the composite material (50 × 90 × 3 mm) is immersed in 2000 mL of ultrapure water, and after ultrasonic waves of 47 kHz are applied for 60 seconds, particles having a particle diameter of 0.5 μm or more from the surface of the composite material are detached. The amount is 5,000 / cm ² or less per unit surface area of the composite material. 如請求項1之導電性樹脂複合材料，其中上述氣相成長碳纖維係將平均纖維外徑為超過5nm且100nm以下之氣相成長碳纖維A與平均纖維外徑為超過100nm且200nm以下之氣相成長碳纖維B混合均質化而成之混合物，該混合物中來自B之氣相成長碳纖維之質量存在比大於來自A之氣相成長碳纖維之質量存在比。 The conductive resin composite material according to claim 1, wherein the vapor-grown carbon fiber has a vapor-grown carbon fiber A having an average fiber outer diameter of more than 5 nm and 100 nm or less and a vapor phase growth of an average fiber outer diameter of more than 100 nm and 200 nm or less. The carbon fiber B is mixed and homogenized, and the mass of the vapor-grown carbon fiber derived from B in the mixture has a mass ratio greater than that of the vapor-grown carbon fiber derived from A. 如請求項1或2之導電性樹脂複合材料，其中上述氣相成長碳纖維與粒狀部形成氣相成長碳纖維結構體，該氣相成長碳纖維結構體具有複數個粒狀部相互立體地以該氣相成長碳纖維結合之網狀結構。 The conductive resin composite material according to claim 1 or 2, wherein the vapor-grown carbon fiber and the granular portion form a vapor-grown carbon fiber structure having a plurality of granular portions which are stereoscopically opposed to each other Phase-grown carbon fiber combined with a network structure. 如請求項3之導電性樹脂複合材料，其中上述粒狀部具 有上述氣相成長碳纖維之平均纖維外徑之1.3倍以上的與圓相當之平均外徑。 The conductive resin composite material of claim 3, wherein the above-mentioned granular member There is an average outer diameter equivalent to a circle which is 1.3 times or more of the average fiber outer diameter of the vapor-grown carbon fiber. 如請求項1或2之導電性樹脂複合材料，其中上述氣相成長碳纖維之纖維外徑(nm)的分布之標準偏差為25~40。 The conductive resin composite material according to claim 1 or 2, wherein the standard deviation of the distribution of the outer diameter (nm) of the fiber of the vapor-grown carbon fiber is 25 to 40. 如請求項5之導電性樹脂複合材料，其中上述氣相成長碳纖維之纖維外徑(nm)的分布之標準偏差為30~40。 The conductive resin composite material according to claim 5, wherein a standard deviation of a distribution of outer diameters (nm) of the fibers of the vapor-grown carbon fibers is 30 to 40. 如請求項1或2之導電性樹脂複合材料，其中使用上述導電性樹脂複合材料而成形之成形物的表面電阻值為10³~10¹²Ω/□。 The conductive resin composite material according to claim 1 or 2, wherein the molded article formed by using the conductive resin composite material has a surface resistance value of 10 ³ to 10 ¹² Ω/□. 如請求項1或2之導電性樹脂複合材料，其中上述導電性樹脂複合材料之斷裂伸長率為40%以上。 The conductive resin composite material according to claim 1 or 2, wherein the conductive resin composite material has an elongation at break of 40% or more.