TW201026777A - Conductive resin composite material - Google Patents

Abstract

The present invention is an electroconductive resin composite material comprising a polycarbonate resin and a vapor-grown carbon fiber, characterized in that the vapor-grown carbon fiber has an average fiber outer diameter exceeding 100 nm and equal to or less than 150 nm; the mixing ratio of the polycarbonate resin and the vapor-grown carbon fiber is 1 to 11.2 parts by mass of the vapor-grown carbon fiber with respect to 100 parts by mass of the polycarbonate resin; and the electroconductive resin composite material has an elongation at break of 30% or more.

Description

201026777 VI. Description of the Invention: [Technical Field to Be Invented] The present invention relates to a conductive resin composite material. [Prior Art] Conductive resin composite materials including tree wax and conductive filler are widely used in the field of semiconductors, electrical equipment, automotive, and aerospace, and their main purposes are to protect semiconductor components from static electricity. Prevents malfunction of precision machines and prevents static electricity and heat accompanying friction by blocking electromagnetic waves. Polycarbonate is widely used as a base resin of a conductive resin composite material used in the semiconductor field or the like, and the reason is that the particles are less polluted, have less outgassing, are excellent in surface finish, and have excellent gloss fluidity. It has excellent koji, excellent recycling and reusability, and it has excellent resin properties. Especially in terms of environmental load or cost reduction, this excellent recycling/recyclability is widely considered to be effective physical properties. On the other hand, as a method of imparting conductivity to the base material resin, a method of adding a material imparting ion conductivity or adding a conductive filler such as metal fine particles, metal fibers, carbon particles, or carbon fibers is added. Its: Ray! In terms of performance and environmental issues, the use of carbon-based materials to impart conductivity is becoming mainstream. Λ 7 In the case of using the particle size (4) ::: in order to exhibit the necessary conductivity? 'It is necessary to add 4 〇 to 5 〇 〇 〇 上述 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 Compared with 142475.doc 201026777, the resin causes a change in the physical properties such as an increase in viscosity, a decrease in fluidity, and an increase in hardness. As a result, there is a cause of poor appearance such as mold transfer property and glossiness during molding and addition of jade, or a decrease in impact resistance. The carbon fiber can also obtain a conductivity having a volume specific resistivity of 1 〇 2 ncm under the condition of adding a 3Qf component, but the fluidity is deteriorated due to a large amount of addition. In recent years, as a conductive filler as described above, a gas phase is being used.

Vap〇r grown carbon fiber. 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 length of micrometers, 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 a few parts by mass of the vapor-grown carbon fiber to a part by mass of the resin from the viewpoint of high conductivity ( Patent Documents 1, 2). PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2, 225, 648. In the conductive resin composite material, the gas phase is formed until the degree of good conductivity is imparted. The long carbon fiber is added to the polycarbonate, and the physical properties and the formability of the resin composite material such as the elongation at break are decreased. The problem when the resin composite material (4) is used to form a target molded article. Moreover, the fibers of the vapor-grown carbon fiber are directly thinner than the two-pole, and the vapor phase of the molten carbon resin is 142475.doc 201026777. The wettability of the surface of the long carbon fiber is deteriorated, thereby causing self-forming of the vapor-grown carbon fiber. The resin composite material is detached. Especially in the field of semiconductors, this is considered to be a cause of failure or damage of semiconductor products. In other words, it is necessary to have a conductive resin composite material having a sufficient electrical conductivity, a resin property such as excellent formability of polycarbonate, and a low exfoliation property of a vapor-grown carbon fiber. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a conductive resin which not only maintains good electrical conductivity, but also has less peeling of vapor-grown carbon fibers and improved elongation at break associated with formability. Composite material. Means for Solving the Problems The present inventors conducted intensive studies to solve the above problems, and as a result, found the following knowledge. 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 1^1 and 150 nm or less, and the polycarbonate resin and gas are used. The content of the phase-growth carbon fiber is 2 parts by mass based on 1 part 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 fibers are less likely to fall off from the conductive resin composite material and have good moldability. 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 3 to 4 〇 nm. Growth in the vapor phase 142475.doc 201026777 When the outer diameter 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. Further, it is preferred that the vapor-grown carbon fiber (fine carbon fiber) forms 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-grown carbon fiber structure having a mesh 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. 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. That is, a 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 peeled off from the surface. The amount of the detachment of 0.5 μm or more is 5 Å/cm 2 or less per unit surface area. If the amount of the detachment is as described above, for example, it is used in the field of semiconductors of the present invention. When the shape is clear, it can suppress the failure or damage of the semiconductor article caused by the detachment. The average fiber outer diameter of the growing carbon fiber is 142475.doc 201026777 1:3 times the average outer diameter equivalent to the circle. Thereby, a strong bond between the vapor-grown carbon fibers can be brought about. It is preferred that the molded article formed by using the conductive resin composite material has a surface resistance value of 1 〇Μ〇 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. More preferably, the elongation at break of the conductive resin composite material is 40% or more '(further, it is above). By using the conductive resin composite material, the moldability at the time of producing a molded article such as injection molding can be further improved. The β-phase-growth carbon fiber is a mixture of a vapor-grown carbon fiber a having an average fiber outer diameter of more than 5 nm and less than (10) nm and a vapor-grown carbon fiber B having an average fiber outer diameter of more than 200 nm and less. The mass of the vapor-grown carbon fiber B in the middle 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. φ Further, the conductive resin composite material can be produced by kneading a polycarbonate resin and a vapor-formed long carbon fiber (fine carbon fiber) at a temperature equal to or higher than the melting point of the polycarbonate resin. Advantageous Effects of Invention 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 detachment of vapor-grown carbon fibers and improved elongation at break in terms of formability. [Embodiment] The present invention will be described in detail based on preferred embodiments. 142475.doc 201026777 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 dimercaptodiaryl compounds are reacted with phosgene, or dihydroxydiaryl A polymer obtained by a transesterification method in which a base compound and a diphenyl carbonate are reacted with carbonic acid, and a representative product is exemplified by 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Polycarbonate resin. As the above dihydroxydiaryl compound, in addition to bisphenol A, there may be mentioned, for example, bis(4-hydroxyphenyl)methane, M-bis(4-hydroxyphenyl)ethane, 2,2-dual ( 4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis & hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3) Phenyl)propane, bis(4-hydroxy-3-tert-butylphenyl)propane, 22-bis(4-hydroxy-3-bromophenyl)propane, 2,2_bis(4.hydroxy-3) a bis(hydroxyaryl)alkane such as ι, i-bis (4-carbyl) such as 5_dibromophenyl)propane or 2:bis(4-hydroxy-3,5-diphenyl)propane. Bis(hydroxyaryl)cycloalkanes such as phenyl)cyclohexyl, phenyl)cyclohexane, such as 4,4,-dihydroxydiphenyl ether, 4,4,-dihydroxy-3,3' a dihydroxydiaryl ether such as dimethyl diphenyl ether, such as a dihydroxy diaryl sulfide such as 4'4-dihydroxydiphenyl sulfide, such as φ n phenyl _3,3f_Dimethyldiphenyl ylide and the like di-diyldiaryl sub-organisms, such as di-m-di-diphenyl, 4,4,-dihydroxy-3,3-methyldiphenyl Dihydroxy diaryl hydrazines such as sulfone . These may be used singly or in combination of two or more kinds. Further, the above-mentioned -diyldiaryl compound may be used in combination with a trivalent or higher compound as shown below. As a phenol with a valence of 3 or more, it is exemplified. Benzene tris, 4,6 dimethyl 142475.doc 201026777 2,4,6-di-(4-pyridylphenyl)-glyoxime, 4,6_2 Methyl-2,4,6-tri-(mono)-p-phenylphenyl)-heptane, 1,3,5-tris-(4-hydroxyphenyl)-benzene, hydrazine-1 tris-(4-hydroxyphenyl) - Ethane and 2,2-bis-[4,4-(4,4,-dihydroxybiphenyl)cyclohexyl]-propane, and the like. The viscosity average molecular weight of the polycarbonate resin is usually from 1 Torr to 1 Torr, preferably from 15,000 to 35,000, and further preferably from 17 Å to 28 Å. The vapor-grown carbon fiber used in the present invention preferably has an average fiber outer diameter of more than 1 〇〇 - " and 150 or less, more preferably 1 〇 5 nm to 145 ❹ nm, and further preferably (10) ~14〇nm. When the average fiber outer diameter of the carbon phase growth carbon fiber is 100 nm or less, the elongation at break of the conductive resin composite material containing the vapor-grown carbon fiber and the polycarbonate resin is not less than 3% by weight, thereby using the resin composite material. The moldability at the time of producing a molded article such as injection molding is lowered. The reason is that the same ❹ f amount is added to the base resin because the vapor-grown carbon fiber having an average fiber outer diameter of 100 nm or less and the average fiber outer diameter exceeds the vapor-phase growth carbon fiber of the above (10). When the number of carbon fibers is increased, the elongation at break of the conductive resin composite is inhibited. On the other hand, when the average fiber outer diameter exceeds (10) (10), the number of vapor-grown carbon fibers per unit volume of the resin composite material becomes 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. In the measurement of the average fiber outer diameter used here, the gas-phase-grown carbon fiber to be measured is firstly scanned by a scanning electron microscope set to a magnification of 35 times, and at least three fields of view are randomly photographed. Then, all of the outer diameters of the fibers measurable in each of the photographic images were measured so that the measurement of the outer diameter of the fibers 142475.doc 201026777 points totaled more than 50 points'. The vapor-grown carbon fiber used in the conductive resin composite of the present invention can measure the fiber outer diameter of about 20 to 50 points in each 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. 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 3 to 4 〇 nm. A conductive resin composite material using a vapor-grown carbon fiber having a standard deviation of 25 to 4 〇 nm generally exhibits an elongation at break of 30% or more, and a vapor-phase growth carbon fiber having a standard deviation of 3 〇 to 4 Å is used. It generally exhibits an elongation at break of more than 5%. 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. Further, it is preferred that the vapor-grown carbon fibers form a vapor-phase-growth carbon fiber structure having a network structure in which a plurality of granular portions are combined. In the structure as described above, the plurality of granular portions are sterically joined to each other by a plurality of vapor-phase-growth carbon fibers. Therefore, it is not a planar branch structure, but has a three-dimensional expansion and expansion, and the granular portion is attached to the gas. The formation of phase-growth carbon fiber is formed during the growth process. Therefore, the plurality of granular portions and the vapor-grown carbon fibers are not connected by appearance only by a binding agent or the like (including a rabbit substance), but the two parts are partially 142475.doc -10- 201026777 Structure of graphite sheet. Thereby, the granular portion is combined with the vapor-grown carbon fiber. The outer diameter of the granules and the outer diameter of the circular phase S which are more desirable for a stronger bond are 1,3 times or more, more preferably 1.5 times or more and 5 times the average fiber outer diameter of the vapor-grown carbon fibers. the following. Sturdy vapor-grown carbon fiber The vapor-phase-growth carbon fiber structure formed into a network by such a strong combination, even if it is added to the polycarbonate by kneading, etc., the structure is also

Waiter to keep. 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. = "In the present specification, the "outer diameter of the granular portion corresponding to the outer diameter" means the measurement of the area of the observed granular portion, and the value of the diameter is determined as a perfect circle. Specifically, an electron microscope is used to image a combination of gas phase growth and mutual energy, that is, a shape of a granular portion, and the image is: using appropriate image analysis software such as winR〇〇f (product) : 'Manufactured by Ergu Trading Co., Ltd.' to trace the area of the wheel of each granular part = out = based on this area, calculate the diameter of each granular part: /, the diameter of the circle, and average it. . It is preferable that the diameter of the gas-phase-growth carbon fiber structure of the flat surface is equal to the average diameter of the area, and the diameter is 2G to 1GG. Here, the area reference "and the diameter" means that the shape of the upper structure is photographed using an electron microscope or the like. In the photographed image, the disc is used to describe each vapor-grown carbon 142475 using appropriate image analysis software. Doc 201026777 The outline of the fiber, the area inside the wheel, the diameter of each fiber structure corresponding to the circle is calculated and averaged. The average diameter corresponding to the circle is judged. The factor of the fiber length of the vapor-grown carbon fiber structure when blended in a matrix of a polycarbonate resin. Generally, the diameter of σ s which is equivalent to a circle is less than 2 〇 _, the fiber length is short, and the use thereof is used. The resin composite material cannot obtain good conductivity, and if it is more than 100 Å, for example, it can be tempered by kneading, etc., when it is blended into a resin matrix, a large viscosity rise occurs, and mixing and dispersion are difficult or Further, the vapor-grown carbon fiber structure has a fluffy structure in which a vapor-grown carbon fiber is loosely formed, and specifically, a bulk density of 0.00 is preferable. 1~0.05 g/cm3, more preferably 〇〇〇1~〇〇2 g/(10)3. If the density is more than 0.05 g/cm3, % ^彳| g # * m (1) is only difficult to make a small amount Adding to improve the physical properties of the carbonated resin. On the other hand, if the bulk density is less than lg/Cm3, the volume of the vapor-grown carbon fiber used is excessively changed: when the composite material is prepared by mixing the carbonated vinegar resin It is difficult to make a problem 4, and it has an adverse effect on the operability. Further, the above-mentioned vapor-phase-growth carbon fiber structure is excellent in particle size, and the graphite sheet having the same multilayer structure::= the second electrical property is excellent. In the invention, for example, it is preferable that the resistance value of the G8 g/e is 〇._~0·025 Q.cm or less, and the powder Q.cm of the powder is better.疋0.005~0.020 Ω, the right shell: J resistance value exceeds °.025 or less than 〇.〇. 5 (10) 'When it is composited with poly-resin resin, it becomes difficult 142475.doc 12 201026777 Producing a composite material capable of maintaining the desired conductivity. Further, it is intended to impart a higher degree to the above-mentioned vapor-grown carbon fiber structure. From the viewpoint of the degree of conductivity and conductivity, it is preferable that the number of defects in the graphite sheet constituting the vapor-grown carbon fiber is small. Specifically, for example, id/ measured by Raman spectroscopic analysis is preferable. The Ig ratio is 0.2 or less, more preferably 0.1 or less. In Raman spectroscopy, a sufficiently large single crystal graphite exhibits only a wave bee (G band) near 1580 cm-1. Since the junction crystal is a limited small size Or due to lattice defects, a peak appears in the vicinity of 1360 cm·1 (D band). Therefore, if the intensity ratio of the D band to the G band (R = Il36 〇 / Il 580 = ID / IG) is below the specific value described above, j, j indicates that the amount of defects in the graphite sheet is small. 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. Further, the conductive resin composite material of the present invention comprising polycarbonate and vapor-grown carbon fibers as described above preferably has an elongation at break of not less than the above, more preferably more than the above. When the elongation at break is 3% by weight or less, the impact strength and the physical properties (adhesive strength) for stretching are lowered. Therefore, when the conductive resin composite material is molded, a brittle molded product is formed. The molded article formed by using the conductive resin composite material as described above has a surface resistance value of 1 〇 M 〇丨 2 Ω / □, more preferably 1 〇 6 〜 1 〇 2 Ω / ϋ. , S is suitable for the parts of the parts used to protect the precision semiconductor parts from static electricity, the floor materials of the manufacturing site, etc. Especially suitable for carrier tapes, etc. 1€ I42475.doc -13- 201026777 (integrated circuit, integrated body, 々, two from ^ ^ integrated circuit) order package or head moving detailed tray. The reason for this is that the transfer oil _ θ from the charged page does not cause an electrostatic short circuit on the part, and is slowly removed by the side of the container & 1 Λ 6 〇 / π (4). When the resistance value of the container is less than 10 Ω/□, the stored φ a 静电 electrostatic core '遽 moves to the container to cause a discharge phenomenon', thereby causing a short circuit of the precision semiconductor component. On the other hand, the surface resistance of the sub-component container is greater than! (7) In the case of (4), the static electricity generated on the surface is difficult to leak, which also adversely affects the part. The vapor-grown carbon fiber structure having the above characteristics is not particularly limited. For example, it can be prepared as follows. Basically, a transitional metal ultrafine particle phase medium is used to chemically thermally decompose an organic compound such as a hydrocarbon by a CVD method (ehemieal ν_d-", chemical vapor deposition method to obtain a fiber structure (hereinafter referred to as an intermediate). Further, the high-temperature heat treatment is carried out. As the raw material organic compound, a hydrocarbon such as benzene, toluene or xylene, or an alcohol such as ethanol, etc., may be used, and is not particularly limited, but in order to obtain the present invention. In the fiber structure, it is preferred to use at least two or more kinds of carbon compounds having different decomposition temperatures as the carbon source. Further, "at least two or more kinds of ruthenium compounds" as described in the present specification do not mean that it is necessary to use 2 Any one of the above is a raw material organic compound. It also refers to the following aspects: in the case of the use of the organic compound in the case of the raw material, in the intermediate-synthesis reaction, 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. Further, in the thermal decomposition reaction system, when two or more kinds of carbon compounds 142475.doc -14·201026777 are present as a carbon source as described above, the decomposition temperature of each carbon compound varies not only according to the kind of the carbon compound, but also It also varies 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 raw material gas, a relatively large combination can be used as the carbon compound. For example, two or more of the following compounds may be selected: acacia or naphthene such as kezhu, keyuan, propyl, butyl, pentylene, hexan, gamma, propylene, cyclohexane, etc. In particular, an alkane having a carbon number of about W; an olefin or a cycloalkene such as ethylene, propylene, butene, pentene, heptene or cyclopentene, especially a dilute hydrocarbon having a carbon number of about 7; Blocks and other fast smoke, especially alkyne with a carbon number of about 1 to 7; aromatic or heterocyclic aromatic hydrocarbons such as benzene, toluene, styrene, xylene, dimethyl, methyl naphthalene, phenanthrene, phenanthrene, etc., especially carbon number An aromatic or heterocyclic aromatic hydrocarbon of about 6 to 18; an alcohol such as methanol or ethanol, especially an alcohol having a carbon number of about 7; and carbon monoxide, _, and lanthanum. In order to use the selected two or more carbon compounds in combination, the gas partitioning is adjusted so that different degrees of knife resolution can be performed in the desired thermal decomposition reaction temperature region or the residence time I3 in the specific temperature region can be adjusted. By optimizing the mixing ratio of two or more kinds of carbon compounds, an intermediate can be efficiently produced. 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 preferable that the molar ratio of the methylate/benzene is set to be a cap, and more preferably 疋1-1 200'. It is 3~1〇〇. In addition, the value is the gas composition ratio at the two ports of the reaction furnace. For example, when using toluene as one of the carbon sources, considering the decomposition of toluene in the reactor, i: i is formed to produce 142475. Doc 15· 201026777 and benzene, you can supply less than enough methane. For example, when the methane/benzene molar ratio is set to 3, methane 2 mole may be added to toluene. Further, as the methane to be added to the toluene as described above, it is not necessary to use only 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. By setting the composition ratio within the above range, it is possible to obtain a two-dimensional network structure in which the gas-growth carbon, the fiber, and the granular portion are all developed into a developed two-dimensional _, _ _ τ 耆 耆Intermediates. It is not necessarily limited, but as a factor for controlling the thickness of the outer diameter of the fiber, the concentration of the smoke compound in the raw material, the concentration ratio of the smoke compound to the catalytic metal in the raw material, and the residence time in the reactor can be used. Therefore, in order to make the outer diameter of the vapor-grown carbon fiber thicker, for example, to increase the hydrocarbon compound in the raw material, the ratio of the concentration of the hydrocarbon compound to the catalytic metal in the raw material is such that the external privacy is such as * < The degree of thickening of the outer shell is superior to that of the molar ratio of the hydrocarbon compound to the catalytic metal, and the box material can bear the ambiguity of the two catalyst metal. In the chemical vapor deposition method (CVD method), it is Ύ丨, w, in order to grow the vapor-phase-grown carbon fiber with the catalytic metal as the core, and the ideal county is to make the metal catalyst used. In addition to hydrogen, in the ambient gas, an inert gas such as chlorine or gas or a transition metal such as iron, bismuth or molybdenum or a transition metallization such as ferrocene or a metal acetate may be used as the catalyst. a mixture of sulfur and thiophene or iron sulfide specific sulfur compounds. As the synthesis of the intermediate, a CVD method of a hydrocarbon or the like which is usually introduced can be used. 142475.doc -16· 201026777 Evaporates a mixture of a hydrocarbon and a catalyst of a specific ratio of a raw material, introduces hydrogen gas or the like into a reaction furnace as a carrier gas, and thermally decomposes 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 intermediates have fibers having an average fiber outer diameter of 100 to 300 nm and are mutually coupled by a catalyst such as the above catalyst. A loose three-dimensional structure that is combined as a granule that grows from the nucleus. The production apparatus including the above reaction furnace is not particularly limited, and for example, a production apparatus having the structure shown in Fig. 1 can be exemplified. In the manufacturing apparatus 1 shown in the drawing, the raw material is evaporated, and the vaporized raw material is mixed with a carrier gas, and the raw material mixed gas is introduced into the inside of the reaction furnace 8, and a mixture of vapor-grown carbon fibers is produced in the reaction furnace 8. . The manufacturing apparatus 丨 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 crucible is connected to the reaction furnace 8 via the raw material mixed gas introduction pipe 7. Further, 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 circumference 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 recovery unit 12 for recovering the produced vapor-phase-grown carbon fiber storage 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 growing carbon fiber recovery unit 12. The thermal decomposition reaction of the hydrocarbon to be a raw material occurs mainly on the surface of the granules which are grown by the catalyst particles or the nucleus which is 142475.doc -17·201026777. The crystallization of the carbon produced by the decomposition is carried out in a predetermined direction by using the catalyst particles or the granules, thereby growing into a fibrous shape. However, the balance between the thermal decomposition rate and the growth rate described in order to obtain the vapor-grown carbon fiber structure m of the present invention is intentionally changed. For example, by using at least two or more 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. Suddenly, the growth of such two-dimensional vapor-grown carbon fibers does not depend solely on the balance between thermal decomposition rate and growth rate, but also on the crystal face selectivity of the catalyst particles, the residence time in the reactor, and the temperature distribution in the furnace. The impact of etc. 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, it is intentionally changed, so that the growth direction of the carbon material is not in a certain direction and is multidirectional, 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. In addition, as a method of efficiently producing an intermediate, in addition to the method of using two or more kinds 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 listed. It is for 142475.doc -18 - 201026777 ^ The method of generating turbulence near the mouth. The term "turbulent flow" as used herein refers to a highly turbulent airflow, which 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, metal catalyst fine particles are formed. This is achieved through the following stages. That is, the first 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 cluster does not function as a catalyst for the intermediate®, and the resulting cluster further aggregates into a metal of about 3 nm to 10 nm by collision with each other. The crystalline particles are used as metal catalyst fine particles for the production of intermediates. In the formation of the catalyst, if there is an eddy current caused by the intense turbulent flow 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 the uniform size of the particles. Metal catalyst particles. Further, in the process of forming the metal catalyst microparticles, an aggregate of metal catalyst particles formed by a large number of metallic crystal particles is formed by the intense collision caused by the eddy current. In this way, the metal catalyst particles are rapidly formed, and the decomposition of the carbon compound becomes larger, that is, the area of the surface of the metal catalyst becomes larger. Therefore, the decomposition of the carbon compound is promoted to sufficiently supply the carbonaceous material, and the metallocene microparticles of the aggregate are used as the core, and the vapor-grown carbon fiber grows radially. On the other hand, if the thermal decomposition rate of a part of the hindrance compound is faster than the growth rate of the carbon 142475.doc -19-201026777 as described above, the carbon material also grows in the circumferential direction of the catalytic particles, around the aggregate. Forming a granular portion, the middle of the three-dimensional structure required. Furthermore, it is generally believed that the aggregate of the upper particles also includes - a portion of the catalyst particles which are less active than the other catalyst particles or which are 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. 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 a plurality of aggregates and accumulations of the plurality of spherical structures are formed. Rather than a simple I 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 a plurality of vapor-phase-growth carbon fibers aggregated or accumulated in the granular portion or a plurality of spherical structures adjacent to each other. 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 firmly bonded to the gas-phase-grown carbon fibers is formed. 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 45 (TC, and is not particularly limited as a specific method for causing a turbulent flow of the gas stream of the material gas. a method in which a raw material gas is introduced into a reaction furnace by a swirling flow or a method of providing a collision portion or the like at a position that can interfere with a flow of a raw material gas that is discharged from a raw material gas supply port into a reaction furnace. As a shape of the collision portion, There is no limit to 142475.doc •20- 201026777. If it is a full flow generated in the reactor due to the full flow generated from the collision part, for example, various shapes of partitions, The ban, the tapered tube, the umbrella body, and the like are used alone or in combination, and are arranged in a plurality or a plurality. In the manufacturing apparatus exemplified in Fig. 1, as an example of the collision portion, a periphery of the introduction nozzle 9 is provided. The rectifying/buffering plate is disposed in the vicinity of the introduction nozzle 9 and is an obstacle that acts as a starting point for the collision of the raw material mixed gas. The obstacle is mixed with the raw material and the turbulent gas generates a vortex to make the temperature distribution and the concentration distribution uniform. The shape of the rectifying/buffering plate is not limited, and the eddy current generated from the rectifying/buffering plate does not disappear. Further, the shape to the lower end side of the reaction furnace 8 may be sequentially formed.

The mixed gas of the catalyst and the hydrocarbon is attached to a sheet-like sheet made of carbon atoms at a temperature of 8 〇〇 to 13 〇〇 β (2: a range obtained by heating at a temperature of 2) Structure. If the intermediate is subjected to Raman spectroscopy, the D band is very large and has many defects. Further, it contains unreacted raw materials, non-fibrous carbides, tar components, and catalytic metals. Therefore, in order to In the intermediate, the residue is removed to obtain a desired carbon fiber structure having a small defect, and the heat treatment may be performed at a high temperature of 2400 to 3000 C by an appropriate method. For example, by using the t-substrate at 800 to 1200 t After heating, volatile components such as unreacted raw materials and tar components are removed, and then annealed at a high temperature of 24 Torr to 3 Torr, to prepare a desired structure, and at the same time, a catalyst contained in the fibers is prepared. The metal is removed by evaporation. In addition, at this time, in order to protect the material junction 142475.doc 201026777, it is also possible to add a reducing gas or a trace amount of carbon monoxide gas in an inert gas atmosphere. + Add the above intermediate to 2400~3 〇〇〇° c When annealing is performed at a range of temperatures, the patch-like sheets made of carbon atoms are combined to form a plurality of graphite sheet-like layers to obtain desired vapor-grown carbon fibers. Further, the above average fiber outer diameter and fibers are obtained. The vapor-grown carbon fiber having a standard deviation value of the outer diameter distribution may be obtained in a single production reaction in the method of producing a vapor-grown carbon fiber, and may be obtained in a single production reaction. A gas phase-grown carbon fiber obtained as a person in a continuous production period of a suitable amount, or a mixture of a plurality of times of the vapor-grown carbon fiber thus obtained. In the present invention, a polymerization in a conductive resin composite material The content of the carbonate resin and the vapor-grown carbon fiber is preferably from 1 to 11.2 parts by mass, more preferably from 3 to 7.7 parts by mass, based on 1 part by mass of the polycarbonate resin. As described above, good electrical conductivity, improvement in elongation at break associated with formability, and reduction in vapor-off growth of carbon fiber from resin composites can be achieved. If the content of the vapor-grown carbon fiber is less than 1 part by mass, the target conductivity cannot be obtained, so that the static electricity generated on the surface of the composite material is hard to leak, and if it is larger than 丨丨·2, not only the conductivity becomes excessive, but also The physical properties of the base material polycarbonate resin are lowered. Further, the exfoliation property of the vapor-grown carbon fiber from the conductive resin composite material is such that the composite material (50×90×3 mm) is impregnated into the ultrapure water 2〇〇〇ml. In the case where the ultrasonic wave of 47 kHz is applied for 60 seconds, the amount of particles having a particle diameter of 0.5 μm or more from the surface of the composite material is preferably 142475.doc -22-201026777 per plex of the composite material. 2500 pieces/cm2 are 5,000 pieces/cm2 or less in the bit surface area. Further, the method for 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 the 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 of being able to use a large-sized twin-screw extruder having a large heat load. As a representative example of the twin-screw extruder, 〇一 &-r company can be cited. As a similar example, TEXW product name, (manufactured by Nippon Steel Co., Ltd.), te, trade name, Toshiba Machine Co., Ltd., ΚΤΧ (trade name, manufactured by Kobe Steel Co., Ltd.), etc. In addition, as a specific example, a melt-kneading machine such as FFM (trade name, company-made U) Kneader (commercial name, manufactured by Buss), and DSM (trade name, manufactured by Krauss-Maffei & Good 疋 is represented by ZSK. In the ZSK type double-extracting extruder, the screw system is completely shouted, and the screw system includes 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 shape of the screw can be two or three threaded screws of J, and it is particularly preferable to use a screw of a two-threaded double-extracting extruder with a wide range of application of the molten resin or the shearing and kneading ability. The ratio of length (X) to diameter (7)) (l/D) is better than 142475.doc • 23- 201026777 is 20 to 50, and further preferably 28 to 42. It is easy to achieve uniform dispersion of L/D, and on the other hand, in the case of excessively large, decomposition of the base resin is likely to occur due to thermal deterioration. It is preferable that the screw has a kneading zone formed by a kneading disc section (or a kneading section equivalent thereto) for improving the kneading property above the crucible, and preferably has 1 to 3. 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. The vent _ is preferably provided to efficiently discharge the generated moisture or volatile gas: a vacuum pump outside the extruder. Further, water, an organic solvent, a supercritical fluid, or the like may be added in order to increase the dispersibility of the gas phase growth, or to remove impurities in the resin composite as much as possible. 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. The method of supplying the vapor-grown carbon fiber to the dispenser is not particularly limited, and the following method can be typically exemplified. (1) A method of independently supplying a vapor-grown carbon fiber and a polycarbonate resin to an extruder. (8) A method in which a vapor-grown carbon fiber = a polycarbonate resin powder is pre-sealed with a mixer such as a high-speed mixer and then supplied to an extruder. (4) A method in which a vapor-grown carbon fiber polycarbonate resin is preliminarily blended and kneaded to be a main particle, and is supplied as a gas phase growth carbon fiber source. In the case of using the vapor-grown carbon fibers having different average outer diameters of the fibers, the vapor-grown carbon fibers may be mixed with each other before the above step (1), and the vapor phase may be grown at the steps (1) to (iii) above. Carbon fiber is mixed with each other 142475.doc -24- 201026777. Further, it is preferable that the above-mentioned conductive resin composite material having a width of 50 mm, a length of 9 mm, and a thickness of 3 mm is immersed in 2 Torr of ultrapure water, and an ultrasonic wave of 47 kHz is applied for 60 seconds. The particle size that falls off from the surface is . The amount of the exfoliate above μ^η is 5 〇(9)/cm 2 or less per unit surface area. If the amount of the detachment is 5000 minus, the failure or damage of the semiconductor article caused by the detachment can be suppressed, for example, when the present invention is used in the field of semiconductors. The present inventors believe that the present invention is the best. The morphological system is a generalized range of the above-described applications, and the representative examples thereof are described in the following examples. Of course, the present invention is not limited to the above embodiments. Preparation of Structure (Rough Diameter)] Using the manufacturing apparatus shown in Fig. 1, an intermediate of a vapor-grown carbon fiber structure was obtained under the conditions shown in Table 1 below, and then calcined in argon gas. As a heterogeneous A _. Then, the center Z is separated, and the pure μ intermediate is subjected to argon gas at 26 〇〇〇c to the ancient field (annealing treatment), and then the gas phase pulverizer is used for the vapor phase growth. The average fiber outer diameter of the carbon fiber is 117 =" The vapor phase growth of the structure and the dimensional structure (Fig. 2 and Fig. 3) are read [Modulation of the vapor-grown carbon fiber structure (small diameter product)] Manufacturing device, After the intermediate of the vapor-phase-growth carbon fiber structure shown in the following Table 1 is obtained, it is calcined in a chlorine gas, and the hydrocarbons are dehydrated as 900 C, and the hydrocarbons such as oil are separated. Pure 142475.doc -25- 201026777. Then, this intermediate was subjected to a high-temperature heat treatment (annealing treatment) at 2,600 ° C in an argon atmosphere, 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 58 nm was formed to form a three-dimensional network structure. [Table 1] Vapor-grown carbon fiber outer diameter, large diameter, large diameter, relative to the unit area of the reactor, the amount of catalyst (mol/m2/min) 0.14 0.38 relative to the unit area of the reactor, the amount of hydrocarbons (m〇l) /m2/min) 13.4 9.4 Carrier gas flow rate (Nl/min) 1250 1850 Raw material input temperature (°C) 400 400 Reaction temperature: upper part (°C) 900 900 Reaction temperature: lower part (°C) 1300 1300 [Example 1 To 100 parts by mass of a polycarbonate resin (Lexan 141R (trade name, manufactured by SABIC Innovative Plastics Co., Ltd.)), 6.38 parts by mass of a vapor-phase-growth carbon fiber structure (large diameter product) obtained as described above was added, and the mixture was uniformly mixed. A ventilated twin-screw extruder TEX-30XSST (trade name, manufactured by Tosoh 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 kneading discs 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 kneading area of the kneading disc and an exhaust port connected thereto are disposed behind the side feeder. The exhaust port of this portion has a length of about 1.5 D, and a vacuum pump is used in this portion to set a pressure reduction of about 3 142475.doc -26 - 201026777 kPa. The extrusion was carried out under the conditions that the cylinder temperature was 300 ° C (the drum from the root of the screw rose substantially equally to the die position), the screw rotation speed was 18 〇 rprn, 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 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 30 (TC). The mold temperature was 80. (:, the rate of fire* was 20 mm/sec, and the molding cycle was about 60 seconds, and a test piece for evaluation was prepared. [Example 2] In addition to vapor-grown carbon fiber structure A test piece for evaluation was produced in the same manner as in Example 1 except that the amount of the addition was 7.5 parts by mass. [Example 3] A vapor-phase-grown carbon fiber structure (a large diameter product) and a vapor phase were grown. The carbon fiber rib structure (small diameter product) is added to the closed tank at a mass ratio of 5 ··1, and stirred for 2 hours or more to obtain a mixture of the vapor-grown carbon fiber structure, and the average fiber outer diameter of the vapor-grown carbon fiber of the mixture is 1 〇 2 nm. A comparison test piece was prepared in the same manner as in the Example except that the amount of the mixture added was 6.38 parts by mass in place of the vapor-grown carbon fiber structure (thick diameter). Example 1] The addition amount of the vapor-phase-growth carbon fiber structure (small diameter product) was 4.17 parts by mass instead of the vapor-phase-growth carbon fiber structure (thick diameter product), which was the same as that of Example 1 except that it was 142475.doc -27-201026777. The test piece for the evaluation was produced. [Comparative Example 2] In addition to the gas-growth carbon fiber structure (thick diameter product), the addition amount of the vapor-phase-growth carbon fiber structure (small diameter product) was changed to 6.38 Å. A test piece for evaluation was produced in the same manner as in Example 1. The physical properties of the test piece for s-valency were measured by the following methods: (1) Surface resistivity is referred to JIS K 7194 (resistance by 4-probe method using conductive plastic) Rate test method) 'Measurement position and measurement method are based on L,resta GP (trade name, MCP_T6 type, manufactured by Mitsubishi Chemical Corporation), UP (trade name, MCP-HT45 type, Mitsubishi Chemical ( (manufacturing)), measuring the surface resistance of the injection-molded test piece (5〇x9〇x3 mm) and shown in Table 2. (2) Elongation at break according to IS〇527-l (general rule) and 527_2 (mold forming, Extrusion and injection molding The test conditions of the rubber were measured for tensile elongation at break. The shape of the test piece for injection molding and the test piece of the size of 18〇527_2 were eight-shaped. The test device was a universal material testing machine (Intesc〇2〇〇5_5 type). The test speed was 50 mm/min, the distance between the chucks was 115 mm, and it was carried out under the test environment of 23: (50% RH). The elongation at break of 5 test pieces which were molded and measured in the same manner as above was calculated. The average value of the values is shown in Table 2. (3) Exfoliation in ultra-pure water in a 3000 mL glass beaker washed with ultrapure water

A test piece (5〇Χ9〇χ3 mm) was prepared by immersing one piece of 2000 mL. Thereafter, ultrasonic waves were applied for 1 minute using 5210E-DTH (47 kHz/140 W) (trade name, manufactured by BRANSON 142475.doc -28-201026777). Then using the microparticles in the liquid to measure

The HIAC ROYCO SYSTEM 8011 (trade name, manufactured by FjACH ULTRA ANALYTICS Co., Ltd.) was used to suck the extracted ultrapure water, and the amount of dust having a dust particle diameter of 0.5 μm or more was measured and shown in Table 2. [Example 2] Example 2 Example 2 Comparative Example 1 Comparative Example 2 Type of large diameter large diameter product mixed product small diameter product small diameter product average fiber outer gas phase growth diameter (nm) 117 117 102 58 58 carbon Weaving fiber diameter standard deviation (nm) 26 26 36 13 13 parts by mass 6.38 7.53 6.38 4.17 6.38 polycarbonate mass parts 100 100 100 100 100 surface resistance value Ω/cm2 6.33 xlO6 1.38x10s 2.75 x10s 5.08x10s 5.23χ103 elongation at break % 40 32 60 27 22 Exfoliation - 〇〇〇〇〇 ※ Mixed product ·.. Small diameter: Large diameter = 1 · · 5 (mass ratio) * Shedding property ... will be dusting at 0.5 μηι or more The gauge is 5000 pieces/cm2 as a reference value (specification value), and the following values are used as 〇. * Fiber outer diameter / fiber diameter... indicates the outer diameter of the long carbon fiber except for the granular portion. As shown in the results shown in Table 2, in Examples 1 to 2 in which the average diameter of the vapor-grown carbon fibers of the vapor-grown carbon fibers of the vapor-grown carbon fibers was more than 100 nm, the results showed sufficient surface resistance values and lower values. Shedding. In the case of 142475.doc •29-201026777, the elongation at break was less than 30% with respect to Comparative Examples 1 to 2 of the small diameter product, and Examples 1 to 2 of the large diameter product were higher than 30%. Also, by . The furnace gives +τ into the 将, the oxygen phase grows the carbon fiber, and the average fiber outer _ coarse gas phase growth carbon fiber structure is mixed with the fine gas phase growth 咴 fiber structure to increase the standard deviation value. :: In Example 3, 'sufficient surface resistance values were also exhibited, and: - diameter - the same low peeling properties of Examples 1 to 2. Especially for _, it has been significantly improved. Elongation at break, industrial availability

The conductive resin composite material of the present invention is extremely useful in various industrial applications such as 〇A (offiee autQmati〇n), electrical and electronic equipment, and the like, and the industrial effect exerted thereon is extremely large.

Further, the conductive resin composite material of the present invention is excellent in electrical properties, improved elongation at break, and vapor-grown carbon fibers by blending the vapor-grown carbon fibers described above in a polycarbonate resin. The character of Luo. By this characteristic, the conductive resin composite material is excellent in crack resistance in the formation of a wide range of conditions, and thus it can provide a conductive material which can be used in a wide range of applications. As such a use, for example, a personal computer, a game machine (a home game machine, a business game machine, a pinball machine, and a slaughter machine =) display device (LCD) can be exemplified. Liquid crystal display, liquid crystal display, organic EL (electroluminescence), electronic paper, electro-polymerization, and projectors, etc., and transmission parts (represented by the cover of the induction coil type power transmission device). Further, as the application, for example, a printer, a photocopier, a scanner, and a facsimile machine (including these multifunction machines) can be exemplified. 142475.doc -30 - 201026777 Further, as such a use, a VTR (video tape recorder), an optical film camera, a digital still camera, a camera lens unit, an antitheft device, and a mobile phone can be exemplified. machine. In particular, the resin composition of the present invention is suitably used for a frame, a casing, and a frame of a digital image processing device such as a camera barrel or a digital camera. Further, the conductive resin composite material of the present invention is also suitable for use in a medical device such as a massage machine or a helium oxygen therapy device; a video recorder (so-called a DVD recorder, etc.),

Home appliances such as audio-visual equipment and electronic musical instruments; game equipment such as pinball machines or horns, and home robots equipped with precision sensors. Further, the conductive resin composite material of the present invention can be used for various wheel 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 (1C card slot, enamel wafer container, glass substrate storage container, head tray, carrier tape, etc.), antistatic or static elimination 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). BRIEF DESCRIPTION OF THE DRAWINGS 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 vapor-phase growing carbon fiber structure produced in the embodiment (5000 times the phase ^ ^ ^) SEM (scanning electron microscope) photograph; 142475.doc • 31- 201026777 Fig. 3 is a 50,000-times TEM (transmission electron) of the granular portion of the vapor-grown carbon fiber structure (large diameter) manufactured in the examples. Microscope, transmission electron microscope) photograph [Description of main components] 1 Manufacturing equipment for vapor-grown carbon fiber 2 Raw material tank 3 Raw material introduction pipe 4 Gas tank 5 Gas introduction pipe 6 Evaporator 7 Raw material mixed gas introduction pipe 8 Reaction furnace 9 introduction nozzle 10 rectification/buffer plate 11 heating mechanism 12 vapor-phase growth carbon fiber recovery unit 13 gas discharge pipe 14 raw material mixed gas introduction port 15 cooling gas introduction port 16 cooling gas outlet 20 metal catalyst particle generation region 30 vapor-phase growth carbon fiber production Area 142475.doc • 32·

Claims (1)

201026777 > VII. Patent application scope: A conductive resin composite material characterized in that it comprises a polycarbonate resin and a vapor-grown carbon fiber, and the average fiber outer diameter of the vapor-grown carbon fiber is more than 1 〇〇11111 And the mixing ratio of the polycarbonate resin and the vapor-grown carbon fiber is 100 parts by mass or less, the vapor-grown carbon fiber is 1 to 11.2 parts by mass, and the elongation at break is 3 0% or more. 2. The conductive resin composite material of claim 1, wherein the vapor-grown carbon fiber has an average fiber outer diameter of more than 5 ηηη and a vapor-phase growth carbon fiber A of 1 〇〇 nm or less and an average fiber outer diameter of more than 1 A mixture of 气相nm and a vapor-grown carbon fiber B of 200 nm or less is homogenized, and the mass of the vapor-grown carbon fiber derived from b is higher than that of the carbon fiber derived from the mash. 3. The conductive resin composite according to claim 1 or 2, wherein the vapor-grown carbon fiber and the granular portion form a vapor-grown carbon fiber structure, the vapor-grown carbon fiber structure having a plurality of granular portions mutually solid The mesh structure in which the vapor phase grows carbon fibers are combined. The conductive resin composite material according to claim 3, wherein the granular portion has an average outer diameter corresponding to a circle equal to or more than 3 times the average fiber outer diameter of the vapor-grown carbon fibers. The conductive resin composite material according to any one of the claims, wherein the standard deviation of the distribution of the outer diameter (nm) of the fiber of the oxygen phase growing carbon fiber is 25 to 40 〇°, 6. In the conductive resin composite material, the standard deviation of the distribution of the outer diameter (nm) of the carbon fiber of the above-mentioned vapor phase growth 142475.doc 201026777 carbon fiber is 3 〇 4 〇. 7. The conductive resin composite material according to any one of claims 1 to 6, wherein the vapor-off carbon fiber is detached from the conductive composite material, and the composite material (5〇χ9〇χ3 mm) is impregnated. In ultra-pure water 2〇〇〇mLt, after applying ultrasonic waves of 47 kHz for 60 seconds, the number of particles having a particle size of 0.5 μm or more from the surface of the composite material is 5,000 per unit surface area of the composite material. /cm2 or less. The conductive resin composite material according to any one of claims 1 to 6, wherein the molded article formed by using the above conductive resin composite material has a surface resistance value of 103 to 1 〇 12 Ω/□. The conductive resin composite material according to any one of the items 1 to 6, wherein the conductive resin composite material has a breaking elongation of 4% by weight or more. 142475.doc