TW200540880A - Electrically conducting resin composition and shaped article thereof - Google Patents

Abstract

The present invention provides an electrically conducting resin composition and the shaped article thereof with excellent electrical conductivity, few ionic impurities produced when extracted with hot water, and with excellent bending property. The electrically conducting resin composition comprises (A) and (B), wherein, (A) is a boron containing carbon type material with nitrogen ingredients not more than 0.2% (by mass) and sulfur ingredients not more than 0.05% (by mass); and (B) is a resin binder.

Description

200540880 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a conductive resin composition having excellent conductivity and excellent toughness, and a formed body thereof. The lead of the present invention is as good as the formed body, and it may be particularly suitable for the test results of the fuel-electric separator. [Prior art] For applications that require high electrical conductivity, conventional metals or metals are used. Excellent. j: Excellent in lubricity, thermal conductivity, durability, etc .: Zicai, and part of the reactivation function obtained by using a combination of carbon materials and polymer materials. Especially with the high ten = to: Hua, Nanji freedom of forming processability, but Yu Yao ;; == dagger mentioned; for a reason in the progressive development. For example, circuit materials, resistors, thinner, hair-receiving components, dust collection filters, and elementary materials can be listed. For this purpose, it is required to have conductivity and high heat resistance. In recent years, based on the viewpoint of environmental issues and energy, in recent years, clean materials have been divided into several types by using hydrogen and oxygen = types. j τ to operate 'the most promising application in automobiles or conventional diffusion batteries is by laminating polymer solid electrolytes, gas oxidation: == to =! will; material gas (hydrogen, etc.) and rolling search In order to separate the early battery isolation film, 200540880 water (water vapor) passage (ditch) was formed. Therefore, for the separation membrane to have such a gas that can completely separate these gases, it is impervious to the internal electricity: Ξΐίΐ and other required separation membrane methods, for example, has been revealed a _ 料 ί = ίί clever manufacturing method (patent document υ, Add adhesive material to carbon ΐ f tf ^ ^? ^ CIP (C〇ld IS〇Static ^ ssing; hardening = participation, hardening treatment 'by performing = = productive ΐ ίSi: 者: more' also have Increasing calcining time requirements, high cost and correction, cutting is necessary, and further progress has become the heart. On the one hand, 'can expect high-volume and low-cost technologies. This is a highly conductive resin composition made from a combination of thermosetting resins such as secret resins and various graphites and graphite. It is used in various patents [KOKAI Publication No. Sho 60_161144, JP Lee Publication 3] Japanese Published Patent Yingli Document No. 28] Japanese Patent Publication No. 48263. Japanese Patent Publication No. 5] Japanese Patent Publication No. 2__33 Brain No .: r Straight! Article 56] Japanese Patent Publication No. 2001-067932 Patent Document 7] Japanese Patent Publication No. __639 200540880 [Patent Document 8 Japanese Patent Publication No. i8 [Contents of the Invention] The surname surname, pond = membrane = which the jj wants to resolve is required. If there are many ionic impurities that require high conductivity and strong corrosion, it is usually washed out by the isolation membrane. It will become a problem and cause the original mold of the film to be degraded or short-circuited. ^ ^ Xi ☆ is working on the t-conductivity 1 ± that can be obtained from carbon and resin composite materials. Poor, there will be the question of forming processing = this, the conductivity of the South, non-corruptible conductive material, discuss a kind of butterfly carbon, material contact fat combination of grease sales composite material. &Quot; Xi κ t ' "At the time of treatment, the stone compound and other elements such as nitrogen are used to make compounds, and 敎 ίίίίΐϊΐϊ pures are also used. Therefore, the impurities in carbon materials are increased. Due to the large number of imperfections, the interface strength with the adhesive resin is also Low, the purpose of the invention is to provide a conductive resin composition or even a body, which can solve the problem of conventional technology. Another purpose is to provide a conductive resin composition and even complex And extracted with hot water There are few ionic impurities and excellent bending properties. As a result of continuous research to solve this problem, the cultivator Yabamoto Kiyoshi, who has decided to solve the problem, has combined specific 3 boron carbon materials and resins. The adhesive was found to be extremely effective in solving this problem, and the present invention has been completed based on relevant knowledge. ',,, that is,' The present invention includes, for example, the following aspects [1] to [12]. 200540880 [1 ,] A conductive resin composition containing: (A) a carbonaceous material having a gas content of 0. 2% by mass or less and a stone claw component of 0.05% by mass or less; and (B) a resin adhesive (« 'The "mass%" is set based on the mass of a boron-containing carbonaceous material containing a gas component and a sulfur component). [2] The conductive resin composition as claimed in item [1] of the patent, wherein (A) the boron in the boron-containing carbonaceous material is from 0.01 to 5 mass%. Detach Yu Yu or [Take a conductive resin composition, where (A) contains carbonaceous nitride nitride (BN) of stone. -5% by mass or less (herein, the "mass%" is set based on the mass of the carbonaceous material containing the NB as a deletion). The conductive resin composition of any one of [1] to [3], which contains 20 to 99% by mass of the carbonaceous material of ϋ 1 and (B) resin adhesive 80 to 1 = ten Mass (quantity U amount ^ base = conductive resin composition determined by the age of M and (B) component to any of [4], wherein the material contains ϋ 格 ϋϋ, the mass ratio of water is 1 to 5 ' At a temperature of 15 ... 12 hours, the conductivity of the water extracted by water is less than or equal to or less than one. The conductive resin composition according to any one of the above, which contains [7] as disclosed in] to [ 6] Electrical conductivity of any = is made of coke, mesophase, green, 'charcoal' = graphite, carbon black, carbon fiber, vapor phase carbon fiber, linoleum contact-Thief II The conductive resin composition of any one of the above [7], the towel ίΒΐ Μ has 0.5 to 80% by mass of the elastomer component (here, m ϊ 3 elastomer component resin adhesive The quality is the benchmark). "", [1 Yicheng Chengna's newly-made conductive tree, such as the conductive molded body disclosed in m, whose towel and body resistance is 0 to less than 5,040,880,880, and Contact resistance is 〇.ΙΩαη2 or less. [11] A fuel cell separator made of a conductive molded body as disclosed in [9] or [1〇]. [12] A fuel cell separator as disclosed in [11] In the film, a groove having a width of 0.1 to 2 mm and a depth of 0.1 to 1.5 mm is formed on both sides, the thickness of the thinnest part is less than or equal to imm, the volume resistivity is less than or equal to 0.1 Ωαη, and the contact resistance is less than or equal to 0 cm2. [Embodiment] Hereinafter, if necessary, the present invention will be described more specifically with reference to the accompanying drawings. (Resin Composition) The resin composition of the present invention contains: (A) a nitrogen component of 0.2% by mass or less, and sulfur Boron-containing carbonaceous material having a content of 0.05% by mass or less, and (B) a resin adhesive. (Boron-containing carbonaceous material) The present invention (A) boron-containing carbonaceous material (hereinafter, also referred to as Γ ( A) Component ") must have a nitrogen content of 0.2 mass% or less and a sulfur content of mass% or less. In the present invention, the nitrogen content is more preferably 0.1 mass% or less, and 0.001 mass% or more, and, The content is 0.02% by mass or less and 0.0001% by mass or more, Furthermore, it is more preferable that the nitrogen content is 0.05 mass% or less, 0.0001 mass% or more, and the sulfur content is 0.001 gree ° / 0 or less, and 0.0001 mass 0/0 or more. The nitrogen component is more than Over 0.2% mass and / or sulfur content exceeding 0.05% by mass, due to the ionic impurities of the Gu body (Gamma is a thief secret) of the conductive resin composition of the application of the present invention, As it becomes more numerous, durability becomes a problem. (Shi Peng) The amount of boron in the component (A) of the present invention is preferably from 0.001 to 5% by mass, more preferably from 0.01 to 4 =%, and most preferably It is 0.02 to 4 mass%. If the rot content is less than 0%, the carbonaceous material with the required high conductivity cannot be transmitted. On the other hand, even if the content of the butterfly exceeds 5 040 880, it is not desirable to further improve the conductivity. Add and delete the source B monomer, b4C, BN, b203, _〇3 and so on, in about 2_ ~ 320 (the gas under TC, ammonia and other pure gas family 3 =. The material is very complicated, Because nitrogen and iit make boron-containing materials in stone anti-shell materials, for example, they can be listed in Yongmeixi R, ^ ^ ^ ^-the content of the added material in the eight I shellfish family _ nitrogen component is not good ——If it is a carbonaceous material, BN will not be formed because it is not a friend. Inactive gas can also be used. The mixture of compounds is not uniform, and not only the rhyme materials become unsuitable. The possibility of partial sintering becomes higher;: powder is inferior = it has a form of ―lower, and it is more suitable to be replaced by a part of ^ special two sons. In addition, carbon atoms ΐ monovalent and carbon atoms The bond may be, for example, in the total (bn) A) fii, 'BN f is preferably α 5 mass% or less, more preferably, G is preferably 0 · ⑽ mass% or less. Β 合 合 詈 0 s ^. 'BN coffee compiled into _, by Ji Ji === (hot water extraction) Water (_ »below): The conductivity of the extracted water (23t under ^^ 12 hours)' Conductivity of hot water extraction water If the rate exceeds 15_e] ^ is _S / em or less. Hot water extraction is not good. KS / Cm 'Due to the durability when forming a molded body 200540880 (powder compaction resistivity) Furthermore, the present invention (A ) Composition, 11 0-05Ω〇, ατ〇, it is best to be 0.02Qcm or less. Tasman two, 〆 文 1 The soil is a 0QQcm because of the poor conductivity when forming a shaped body] If the resistance coefficient exceeds _ Qcm, (raw material of (A) component) Mesophase carbon, pitch charcoal Raw materials of this component 'can be cited: from coke, wood, resin, carbon black, carbon fiber, helmet ^ natural graphite, gas phase carbon fiber too', Almost graphite, artificial graphite, or a combination of two or more of them. Graphite selected from the group of Doujin and alkenes, 1, Gas phase: Carbon: = tube =, carbon black, natural reason The combination of coke, mesophase carbon, carbon, A: 5, out. Better combination. In order to advance-i contains :: more;; fi fiber two carbon nano coffee ^ carbon fiber, carbon nano The selected method is to obtain the artificial graphite by carbon phase, carbon black, and gas phase method (artificial graphite). The raw materials are carbonized to make coke.:, Media pitch, etc. =: ir ,backward

Shape i; is to add the adhesive to the graphitization treatment of coke and powder 4 and: === coke 予). X. Light heating treatment is preferably eight, below _C, below the set value, Greek Double to A — heat treatment for the word lice formation, the sulfur content is set to chemical treatment, etc .: graphite body in an inert gas-type inert gas environment, but if it contains boron, it is bonded to nitrogen to generate 200540880 BN is not good. (Carbon black) Examples of the carbon black of the (A) component raw material include Kechain carbon black obtained by incomplete combustion of natural gas and the like and thermal decomposition of acetylene; thermal decomposition of acetylene carbon black, hydrocarbon oil, or natural gas. Furnace carbon black obtained; thermal carbon obtained by thermal decomposition of natural gas and the like. (Carbon fiber), the carbon fiber can be exemplified by bitumen made of heavy oil, byproduct oil, coal coke, etc., and PAN series made of polyacrylonitrile. (Amorphous carbon) Examples of the method of forming carbon include a method of making the desired resin hardened and then calcining the powder to make it too strong; or a method of forming a powder on a spherical or amorphous powder and hardening the phenol resin and then performing a calcination treatment. Etc. In order to obtain the conductive south amorphous carbon, it is more suitable to perform heat treatment above Gangnao. (Month Plague Graphite Powder) The black ink powder can be exemplified by degrading sulfur by using graphite, such as: The graphite is impregnated in a mixed solution of concentrated sulfuric acid and phosphonic acid, and the compound layer between the concentrated graphite layers is formed to be pulverized or pulverized, and the powder is temporarily rolled into a sheet shape (gas phase carbon fiber). Phase-method carbon fiber is obtained by using compound as-, in Ferrocene et al. 14 on the day 12 200540880 = thermal decomposition reaction with hydrogen, the fiber diameter is about 0 ~ 5, and nont ^ = 2300 ~ 32〇 (rC is graphitized.) In the case of thermal decomposition reaction, in the case of non-sexual milk, non-smoke n2, it is more suitable to use fresh blunt gaseous elemental gas. (Carbon nanotubes) Remaining rice tubes not only have mechanical strength, field transmitter energy or hydrogen absorption. Mi is also called sundial, and magnetic properties have also started to attract attention. Carbon nano ^ is also called graphite sunburst, filamentous carbon, graphite fiber, ultra-thin carbon tube, nitrate, ^ medium carbon carbon nano fiber, etc. The fiber diameter is about; ~~ 12: s machine Si degree rice tube is better 'because it has (23 ^ ° carbon (J meter tube ^ has been revealed in Saito Bandong "basis of carbon nano tube" inactivity) _ == ^ 录 _ΰ ~ _ of the thief elements (granularity) or grading, etc. ====== to adjust the necessary physical grading, etc., it is better to use heat treatment to smash or adjust. If in After the heat treatment, pulverization is performed, because the ===== (pulverization and polarization) pin mill (hammer mill, W (rotary hybrid, wire mill, 13 200540880 planetary mill), stirring Type mills (bead mills, ultrafine mills, flow tube mills, ring mills), etc. In addition, the sieve type of the micromill is selected. It is possible to use the conditions of the turbine's mill, ultra-micron mill, and jet mill. Use ^ pulverizer for pulverization. At this time, the selection of the pulverization conditions and the advancement of the rod to the eighth level if necessary to control the average particle size and particle size. The method of material classification by the final knife, as long as it can be separated, any method can be used, for example, sieving method or forced vortex centrifugal classifier (micron isolation membrane, turbine Purex (Purex), Turbine classifier, ultra-isolated membrane), inertial classifier (improved vertical impact machine, curved tube jet), etc. Air flow classifier. In addition, φ can also use wet precipitation separation method or centrifugal classification method. (Heat treatment ) The heat treatment can be exemplified by sufficiently mixing the raw material and the boron source to be homogeneous. After the powder is put into the crucible, the method of using an Adeson furnace which is energized; using a high-frequency heating furnace, Method for heating powder by graphite heat sink. The processing temperature is about 2000 ~ 3200 ° C, and it is heated in an inert gas-type inert gas environment (resin adhesive). If A /) is a carbonaceous material containing pentene and a lime tree ( , × Τ ^ ^ (Β) 0},. Xie is not particularly limited. For example, this adhesive can be listed as: thermoplastic tree month, thermosetting resin. (Thermoplastic resin), Chengqiu plasticity 1 Examples: Polyolefins (polyethylene, polypropylene, ethylene-propylene CABS cutter, PVC, acrylonitrile-butadiene-butadiene ethylene copolymers), polyethylene resin (PMMA), polyethylene Imine (PI), liquid crystal polymerization 14 200540880, polyetheretherketone (PEEK), fluororesin, polyacetal (POM), polyamidoamine (PA), polyethylene terephthalate (PET) ), Polybutylene terephthalate (PBT), polycarbonate (PC), cycloolefin polymer (COP), polyphenylene sulfide (pps), polyphenylene ether (PPE), polyphenylsulfone (PES) ) Etc. Among these, polyolefin, polystyrene (PS), acrylic resin (PMMA), polyimide (pi), and liquid crystal are more preferable from the viewpoint of water resistance and heat resistance. Polymer, polyether ether snapper (PEEK), fluororesin, polybutylene terephthalate (pbt), polycarbonate (PC), cyclic olefin polymer (COP) 'polyphenylene sulfide (pps), Polyphenylene ether (PPE), polyphenylsulfone (PES).

(Thermosetting resin) Examples of the thermosetting resin include a phenol resin, an unsaturated polyester, an epoxy resin, an alkylene resin, an alkyd resin, an acrylic resin, a melamine resin, dioxin, and Amino resin, phthalic acid phthalate resin, dipropionate resin, furan resin, ammonium resin, urethane resin, urea resin, etc. It is also preferable to use phenol resins, unsaturated polyesters, epoxy resins, vinyl esters, dilute propyl acetate resins, and 1,2-polybutadiene, and one or more of them may be mixed. (Suitable resin) In the fields of humans and adhesives, because of the resistance of the epoxy resin and lipids to the phenol group, it is more preferable to use resins with bisphenol A type and backbone, such as fats, or Diene-based molecular diene and the like. Psylla spp., Phenol resin, vinyl ester resin, or 1,2-polybutylene (composition ratio) The composition of the samarium component and the samarium component of the conductive resin composition of the present invention 15 200540880 ratio, (A) component: ( B) Ingredient surface ^%), more preferably (3G ~ 95 mass: ⑽ ~ 1 mass mass%): (50 ~ 8 mass%, taxi, berry 0), dare to be (50 ~ 92 found high conductivity If the other two points are less than 20% by mass, it will not be difficult or inferior. On the other hand, if it exceeds 99% by mass, it will become difficult due to processing (elastomeric component). It is better to include the component (B).仏 ⑽ Knife, more preferably 1 to 80% by mass, and most preferably 2 denier ^% elastic body composition, the elastomer component becomes jealous 葙 from L 5 berry%. If less than 0.5 mass butyl rubber, Ethylene-propylene-diene terpolymer copolymerized rubber, ethylene i ΓΪίί, olefin rubber, chloroprene rubber, urethane rubber, poly ί: special η ethene rubber, olefin rubber, epichlorohydrin rubber, original Spinene ^ ^, butyl rubber, styrene-based thermoplastic elastomer, olefin-based r r; r acid vinegar, plastic elastomer, polyacetate-based thermoplastic Elastomer, thermoplastic elastomer two female Mi, 1,2_ polybutadiene-based thermoplastic elastomer, a fluorine-based heat-i elastomer, soft acrylic resin or the like. Such a polymer may? Be

It is used by combining two or more types. $ AJ Among these polymers, from the viewpoint of water resistance, acrylonitrile ~ butadiene rubber, hydrogenated nitrile rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-dilute binary Total & synthetic rubber, acetylene-butene-ene rubber, isoprene rubber, acrylic rubber, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer ^, 1,2-polybutadiene-based thermoplastic elastomer Body, fluorine-based thermoplastic elastomer, soft resin. , 16 200540880 (additives) Lightning guide: In the conductive resin composition of invention 1 and ΐ, for the purpose of improving the hardness, strength, Li shape, durability, weather resistance, and financial properties, etc., you can also use Crystal fibers, metal oxides, organic fibers, UV stability. Shrinking agents ^ _ Release agents, lubricants, water repellents, thickeners, low-yield additives such as hydrophilicity imparting agents. First (method of manufacturing resin composition) and machine case t'if hair: The conductive resin composition of the moon can be prepared by uniform ageing in a roller, an extruder, a scale exposing, and planetary mixing. Marriage and saki machine 'supply the materials of each ϊϊ shape machine or mold' to make it easy for the purpose of eclipse recognition „1 from Ding from powder or granulation. Crushing, you can machine, contour Rotary pulverizer (over-type mill, pin mill (formed body)

Sff ° ^ ΙΙ ^^ ΤΤΙΙ: 17 200540880 The body is rolled with a roller or a calender. In addition, it is more preferable to perform the wrapping in a vacuum state to form the voids of the towel or to perform the molding to obtain a molded body. In order to obtain I: Erli = vacuum is formed in the forming. Ding I ,,, Yue 丨 The good mouth is better, it is more suitable to make the mold groove (the physical properties of the molded body) 〇 Guide = ^ formation of fat composition _ volume electricity _ number is more appropriate if the product resistivity exceeds αΐΩοη, because Under the beam. Poor system. Do n’t want to be “admiral limited”

It is preferable that the contact resistance of the formed body of the resin composition with carbon paper is less than o.mcm2. 005W is limited. In the field of requirements, (the separator for fuel cells) will be formed into a T-shape method, injection molding method, casting method, injection compression molding and the empty state H is better for forming. 'Make the mold_whole mask to form a true, shrink-form, based on the view of Shengniu, it is more appropriate to use multiple molds. It can be formed by multi-layer compression (lamination), with a small output. In order to improve the surface accuracy of a flat product when it is new, as described above, the sheet is first formed and then compression-molded. In terms of injection molding, in order to further improve the moldability, carbon monoxide gas is injected from the middle of the opening and closing machine, or it can be dissolved into the material and the bottom can be used to form the electrical resin composition to form a fuel cell. There are no specific restrictions on the method of the separation film (starting from the film). For example, 18 200540880 A method of forming in a supercritical state. To adopt the injection compression method. Injection compression method; ^ surface accuracy, it is more suitable to close the injection after injection; 1 / side close two open ^ mold state, the method of entering; and the method of closing the closed mold's injection method, etc. . After the thinning force of the U game becomes zero, the mold clamping pressure is applied to the mold used, although there are no restrictions. For example, a heat-insulating mold that puts a heat-insulating layer into a mold slot is used. Another). == 3 methods can be listed: add translation by induction. The temperature can be selected according to the type of the composition, and the optimum temperature can be selected. The temperature range of Π ~ 200 C 'moderately determines the range of 10 ~ 1200 seconds. The feeling of 2 products Γ may be cooled, but this method does not stop forming: Second,. For the purpose of suppressing bending, use the cooling plate clamp I to open and enter the cold_ method; or, even the mold— The method of cooling the money (shape of the separation film, etc.) The insulation film for the passage combustion must be formed by a borrow method to allow gas to flow on both sides or one side. In order to make the path of the gas flow can be formed by the mechanical protection of the day by day, the channel is formed. (Ditch coffee, the cross-sectional shape of the channel or the shape of the channel by pressing the isolation membrane is not particularly limited, such as The cross-sectional shape of the road can be exemplified by a rectangle, a trapezoid, a triangle of 0.1 to 2 mm, and a depth of 0 w 5 mm. The thinnest part of the separator of the present invention is preferably 1 mm or less. More preferably, it is a8 mm. 19 200540880 If it exceeds 1mm, it is not good due to the weight of the unit cell. (Physical properties of the separator) The volume resistance of the separator of the present invention is less than 0.05Qcm, preferably 0, = It is 0 · 1Ω · or less. It is more preferably ， cm. For applications that require high electrical conductivity, ^^ is subject to electric power and if it exceeds the good A, the fine resistance of fine and carbon paper is preferably less than aiw. More ribs m, worrying about the electrical requirements of the field, will be limited. (Applications) In addition, because the model is easy to form, the electrical conductivity or thermal conductivity of the fields outside the guide of the present invention can be improved. Α 于 ㈣ 梦 ΐί 优 ^ 的 'can get extremely high performance Therefore, it is useful for various applications of various components such as collars, machinery, vehicles, etc. There are various types of battery current collectors, electromagnetic wave shielding materials, and electrode dispersion .... , Semiconductor parts, bearings, PTC elements and brushes [Examples] Limitations ϊ —__ This invention, this invention is not the following shows the production method of carbonaceous materials used in Examples, Comparative Examples. (A) Ingredients · Carbon Material χ / < A1 > · 3 rods of graphite micropowder (impurity bn contains 0 to 5%) MC ^^^ HrkaWaMieiOn (shares)) MC made of non-needle coke (moon and wound) Coke is coarsely pulverized to a size of 2 to 3 mm or less. Using a jet mill (IDS2UR, made by Japan's New Magic (stock)), 20 200540880 = coarse crushed product finely crushed. After that, it is adjusted by classification. The shed turbine classifier (π ·, manufactured by Nippon Engineering Co., Ltd.) is removed into particles of about 5 μm or less to perform air flow classification. The carbonized plutonium was added to the finely pulverized coke obtained by adding 14.85 kg, and mixed with Henschel ~ Scrambler 'at _rpm for 5 minutes. 1kg of it was enclosed in a volume of 5 liters of attached graphite hanging magma, and placed in a graphitization furnace using a graphite heater. The furnace was vacuumed at the end, and then replaced with argon gas at an internal pressure. 12 MPa argon ambient gas was used to perform graphitization at a temperature of 2800 C. Then, it was left to cool in an ammonia atmosphere, and the powder was taken out to obtain 0.94 kg of powder. The average φ average particle diameter of the obtained graphite fine powder was 20 μηι, and the nitrogen component was not detected. < Α2 >: A mixture of gas phase carbon fiber (hereinafter referred to as "VGCF". Registered trademark of Showa Denko) and A1 (graphite fine powder). 0.75 kg of VGCF and 0.15 kg of carbonized petrochemical (b4C) were added. In 14 lkg of this A1 finely pulverized coke, use a Henschd mixer to mix for 800 minutes at $ 800. 1 kg of it was sealed in a graphite crucible with a capacity of 1.5 litres and placed in a graphitization furnace using a graphite heater. After one end of the furnace was vacuumed, it was replaced with argon and the internal pressure was 0.12 MPa. Graphite at a temperature of 280 ° C under an argon ambient air flow, and then left to cool in an argon atmosphere and take out the powder to obtain a powder of Lu. The average particle size of the obtained graphite fine powder is 15 μm, The gas component is not finely powdered by the ink) < Α3 > Carbon nanotube (hereinafter referred to as "CNT") and A1 (mixture of stones ~ 0.75kg of CNT obtained by the following method (the manufacturing method is disclosed below) Add 0.15 kg of boron carbide (Bf) to Rlkg of this A1 finely pulverized coke, ^ Mix it with a Henschel mixer at 800 rpm for 5 minutes. Then seal 1 kg of it into a 1.5-liter graphite crucible with a lid. Place it in graphite = 使用 using a graphite heater, vacuumize one end of the furnace, and replace with argon. ， Pressure 2 Τρ: 21 200540880 i Graphite at the prevailing war temperature, and then place it in The powder was taken out after the argon was passed to obtain 0.94 kg. Powder. The average particle size of the obtained graphene powder was 12 Å, and the nitrogen component was not detected. ≪ Method of making CNT > In graphite rods with a red diameter of 6 mm and a length of 50 mm, starting from the tip, A hole with a diameter of 3 mm and a depth of 30 mm at the center is made by mixing a mixture of rhodium (position): platinum (pt): (C) with a quality ratio of 丨: 丨: 丨 into this hole. = Pole. On the other hand, a cathode with a diameter of 13 faces and a length of 30 faces made of graphite rods with a purity of 99.98% by mass is produced. These are arranged in a reaction container in the opposite direction, and the power source is used. Then, purity is used. Vol% helium replaces the gas in the reactor ^, and performs direct current discharge f. After that, as the deposits in the reaction zone, the coal (cavity coal) on the inner wall and the coal (cathode) deposited on the cathode, the current is between _TGrr and 7GA τ. During the reaction, the interval between the cathode and the cathode is 1 to 2 mm. The recovered coal series is placed in a mixture of water and ethanol with a mass ratio of 丨: 丨 and the ultrasonic wave is used. Disperse the test of the thief, and then turn to cry = solvent, and then disperse this sample in the ultrasonic Ionic interface activity was reduced to αm% aqueous solution of methylene chloride, and then centrifuged at 5 (φ) for 3 (2) centrifugation to recover the dispersion. Furthermore, by using 35 (rc in air, And refined 'to obtain a stone anti-residence tube with a fiber diameter of 1 to 10 nm and a fiber length of 0.05 to 5 μm. ≪ Α4 > Boron-containing graphite fine powder (bn content: 0.7 mass%) 1 kg of boron carbide (Gen0 was added to 14 kg of the A1 finely-pulverized carbon, and mixed with a Henschel mixer at 800 rpm for 5 minutes. Then, it was sealed, I. 5 liters, and the covered Shi Jicai was placed side by side in a graphitization furnace using a ^ ink heater. Under an argon gas flow with an internal pressure of 0.103 MPa, it was carried out for 2800. < t Graphitization. After leaving it to cool in an argon atmosphere, the powder was taken out. 22 200540880 The average particle diameter of the final test was ΐ8μίη, and the nitrogen component was analyzed. The shellfish, if converted into BN, contained about 0.7 mass%. < Α5 > Boron-free graphite micropowder coke ', the A1 pulverized powder is placed in a graphite hang-up with a lid and a U liter of graphite, and heated by ink! Take 3Γ ° at the internal pressure coffee, and then graphitize it at the temperature, and then put it in argon "Jing" 均 »the average particle size is 21 qing, the result of the atmosphere composition, and imr out the ink coffee powder + fiber ( Hereinafter, it is simply referred to as "VGCF." Showa Denko Electric (it is a mixture of graphite fine powder) (content of VGCF) and ai5kg of carbonized masterbatch (bw) were added to 14 lks $ A 丄 = crushed coke. H_h person; 2 33 ^ enclosed in graphite with a volume of U liters and ΐ === internal pressure. • Nitrogen ambient gas: • When powder was produced, 2 kg of ‘: But age ^ 14 qing’ was analyzed. As a result of analyzing the nitrogen component, the final BN contained about 58% by mass. Change the right to # to display various characteristics of the carbonaceous material in Table i. 23 200540880 [Table Π Properties of carbonaceous materials

Powder compaction resistivity (pressing direction) | Methods for measuring various properties of carbonaceous materials are shown below < Average particle size >, 50 mg of sample (carbonaceous material), 5_ of steamed water +: person · A 2% Triton (surfactant) aqueous solution in ml was subjected to two-wave dispersion, and was determined using Micrtrack HRA I manufactured by Nikkiso Co., Ltd .: < Nitrogen content > Gasification method), Yu Zhongzhongdan (carbonaceous material) 'in the water vapor stream to add _ points = $, sample = Γ to receive ammonia reading in the area, and then paste sulfur, ^^ = Chu sat to find the relative Nitrogen was quantified at the percentage f of the anhydrous sample.仃 滴 疋 '< Sulfur content > In accordance with JIS M8813 (high temperature combustion method, on quartz plate material), heated in an oxygen stream to about 13 delays, sulfur yellow = oxygen charcoal 24 200540880 water solution After it was absorbed, the measurement of vermiculite ▲ ion was performed by anion chromatography, and converted into sulfur concentration in the sample. ≪ Boron content > Two * separation materials 'add sulfur acid' to decompose the product (3, method) of microchloric acid (Ηα〇4), and further dilute with water to add the solution, and determine the amount of deletion. Bayi 'then placed this dilution at 1 cp for luminescence analysis < BN content > < Conductivity of hot water extraction water > Decomposition with pressure, (2 pS / Cm or less), 9: (-: 〇 (Made by Yanako), measure 45g of pure water at 150 ± 0.5 ° C and correct it. The salt material (carbonaceous material) of 8 was sealed and placed at room temperature (2Vr, phase was extracted for 120 hours. After that, it was cooled to a __A system _meter < powder compaction resistivity > The coefficients are measured using the device shown in Figure 1. 5, 5 and 5 are copper lightning arresters / systems, and are made of insulating resin. The four-terminal method / system voltmeter of Figure 1 The current generates a power source. The resistivity of the sample is measured by using the compression formula of the compression rod 4, “彳”. The current 1A is compressed from the electrode and pressurized to 1 MPa. The voltage between the terminals of the constant current measurement 5 (pressurized) Direction). With the terminal Γ, (). Set the resistance of the sample (between terminals) to & (Ω), 25 200540880 = v2 / i2 is established. In this way, the vertical direction of f can be obtained. Cross-sectional area (cm2); L2 •• Terminal Bu; [, distance between: f 方 方 二 ^ 定 上 丄 The sample is tied to a square with a bottom surface of 3cmx3em, cm. In a firm state, the height becomes 3 ~ — generally Filling the sample and measuring it plus f—Example 50Clt (Proportion of Model made by Japan Toyo Seiki Co., Ltd.) 5 minutes of raw materials in 5 minutes: The ingredients and groups shown in Table 2 are 100 faces, 0 to 2mm flat and f, and the: is poured into a 50t compression molding machine that can be made into a temperature shoe and a pressure of 15Mpa, but compressed. It is hardened at a temperature of 40 ° C and a pressure of 15MP. After that, the job is obtained by cold. The characteristics are shown in Table 3 after being touched and cooled for 2 minutes. (Unit: mass%

26 200540880 Butadiene (1) · 13000 (Molecular weight · 3000, 1,2-bond · 91.7%, viscosity: 107 Pa · s (5 (rc), polybutadiene) (2) ·· JSR company made _810 (MI ·· 3g / min (150 ° C, 21.1N battle weight), 1,2_ Bonding: 90%) tVB • Monovinylbenzene 'Japan New Day DVB-960 (95% to 97% by weight of divinyl) manufactured by Tie Chemicals Corporation.

Hardening initiator: 2,5-Difluorenyl-2,5_di (t_butylperoxy) Perhexa25B

Table shows that the obtained formed body contains a carbonaceous material having a low nitrogen content, a low nitrogen content and a high sulfur content, and a carbonaceous material such as B **, which can obtain high electrical conductivity and excellent bending characteristics. There are almost no ionic impurities. On the other hand, as in Comparative Examples i and 3, although there is a certain point, if a lot of impurities are produced, the conductivity of the hot water extraction water will be high, and the bending characteristics will also be poor. In addition, as in Comparative Example 2, the electrical conductivity also deteriorated. Example 4 and Comparative Example 4 Using a Laboplast mill (godei 27 200540880 50C150 manufactured by Toyo Seiki Seisakusho Co., Ltd.) ′ The raw materials were mixed at a temperature of 90 ° C and 35 rpm for 4 minutes. . The composition of each component and the blending ratio of 100mmxK) (W2mm flat plate) is poured into a mold that can be made at a temperature of 180 ° C, at a pressure of 15 MPa, and a 108 J f1 compression molding machine is used. The rear section of the hard wire is made into a bump. It is decent (unit mass ° / 〇

Carbon quality goes to A4 I — ~ --- I. Galicium sylvestris made by Showa Polymer Co., Ltd. ^ EPicron EXA4850_150 made by 1nk Chemical Industry Co., Ltd. • Dibenzylphosphine, special grade made by Japan Pure Chemical Co., Ltd. Test reagent purity 98 · 50 / 〇 [Table 5] Physical property coefficient rate Electrical conductivity of effluent unit mQcm J ^ cm2 MPa GPa Example 4 4.5 3.3 78.0 13.2 1 · 0 23 Comparative example 4 5.3 4.1 62.6 12.4 0.71 103 28 200540880 5, in the obtained formed body, containing Shi Peng, ^, • Excellent If Trotter is a carbonaceous material with almost no BN, electrical conductivity can be obtained, with little sulphur content, and almost no ions when extracted with hot water Sexual impurities. In the other direction, it is excellent in bending characteristics. It uses a carbonaceous material with a lot of impurities, and it extracts rhenium with hot water, and it has poor rheology.卞 Take out the conductivity of water _ Examples 5 to 8 and Examples 5 to 9 Using a Laboplast mill (by the way of Toyo Seiki mechanism, at a temperature of 20 ° C, 35 ° C, Table: Model ratio of U The raw materials are mixed for 5 minutes. The mixed mold is pressed on a flat plate 5Gt compression molding machine and preheated; after that, it is heated at 15 minutes and added i I, and the knife holder is held. That is, at a pressure of 15 MPa and a temperature of i35 ° C: for t minutes, using cooling and compression, at a temperature of 60 ° C and a pressure of 15 MPa; and cooling for 2 minutes to obtain a molded body. The characteristics of the obtained molded body Is not shown in Table 7.

(Unit mass ° / 〇

H-SBR SEBS $ carbon material A1 0.74 0.74 0.74 0.74 0.74 85.24 0.74 85.24 carbon material A2 warm material A4 carbon material A5 carbon material A6 85.24 85.24 85.24 85.24 85.24 85.24 85.24 29 200540880

PP: polypropylene, San Alomar PX20IN SEBS manufactured by San Alomar Company: styrene ethylene-butene_styrene block copolymer, Cleyton Polymer

Cleyton G1652 by Japan

H_SBR: Hydrogenated styrene butadiene rubber, Dainaron 1320P manufactured by JSR Corporation [Table 7] Physical property unit Example 5 Example 6 Example 7 Example 8 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Volume resistivity mQcm 3.5 3.2 3.8 3.5 7.1 30 5.6 6.8 6.4 Contact resistance mQcm2 2.4 2.1 2.8 2.6 5.6 14 5.0 5.2 4.9 Flexural strength MPa 56.1 57.1 55.4 57.3 50.1 57.2 56.1 51.2 52.3 Flexural modulus GPa 8.4 9.6 9.4 10.1 9.8 10.6 10.2 10.1 10.4 Bend and skew ° / o 2.0 1.8 1.9 1.7 0.94 1.1 0.91 0.89 0.85 Electrical conductivity of hot water extracted by hot water pS / cm 26 25 21 20 102 32 93 92 89 k According to Table 7, the obtained formed body contains boron and nitrogen A carbonaceous material with few components and sulfur components and almost no BN can provide high electrical conductivity, excellent bending properties, and almost no ionic impurities with hot water extraction. On the other hand, as in Comparative Example 5, it is also worsened. If carbonaceous plutonium with a lot of impurities is used, the conductive Γ 热水 Γ f of the hot-water extraction water becomes worse. In addition, as in Comparative Example 6, if Shi Peng is not included, the conductive examples 9 to 10, and the comparative example ~ η = 东洋 精 # Mechanism riding A " 広 度 M00 35 ', each component shown in Table 8 is detailed And point 5 minutes off the raw materials of the case. This turbulent can be poured into the mold of a flat plate = 30 200540880 Κ) 0πιπι > ^ 00ιηιηχ2ηιηι, using a 50t compression molding machine, and preheating at a temperature of 220 C for 3 minutes, and then a pressure of 15MPa Next, score 2 points. The bell is heated and pressurized and maintained. Next, it was maintained at a pressure of 15 MPa and a temperature of 140 ° C for 5 minutes, and then cooled and compressed, and then cooled at a temperature of 40 ° C and a pressure of 15 MPa for 2 minutes to obtain a molded body. Table 9 shows the characteristics of the obtained molded body. [Table 8] Cluster _____ (unit mass%) Example 9 Example 10 Comparative Example 10 Comparative Example 11 PVDF 23.75 23.75 23.75 23.75 Acrylic resin 1.25 1.25 Fluoroelastomer 1.25 1.25 Carbonaceous material A1 75 75 I Carbonaceous Material A4 75 75 PVDF: Polyvinylidene fluoride, NefmnVW-410 acrylic resin manufactured by Daikin Industries, Inc. · Parapet SA-FW001 fluorine elastomer made by Kuraray: Daiel Thermoplastic T-530 manufactured by Daikin Industries, Inc. [【 Table 9] Physical property unit Example 9 Example 10 Comparative example 10 Comparative example 11 Volume resistivity mQcm 4.3 4.1 7.8 7.2 Contact resistance mQcm2 3.1 3.2 4.3 4.1 Flexural strength MPa 65.3 1 62.1 60.8 61.3 Flexural modulus ^ ~ GPa 9 ^ 8 ~ ~ 9.2 10.1 '10.3 Bend and skew ° / o 1.6 1.4 0.89 0.82 Electrical conductivity of hot water extracted pS / cm 32 28 110-107 31 200540880 Table 9' In the obtained formed body, there is almost no BN carbonaceous carbon. If it is made of materials, it has low nitrogen content, low nitrogen content and sulfur content, and it is almost silky when extracted with hot water. It has a high level of flexibility and excellent f-curve characteristics. Use a carbonaceous material with many impurities. Sex also changes difference. The conductivity of the simmering water becomes high and the bending characteristics are high. Example 11 and Comparative Example 12 Ship-day machine, the raw materials in the proportion of _ made _ are mixed for 5 minutes. Pour the ingredients and the composition of the plate of 100mmxK) 〇ηιιχχ_ into a wide stirrer that can be made at a temperature of 320 ° C for 3 minutes in a pre-forming S'H50〇t shrink molding machine, heat and pressure for 2 minutes, and To maintain. I, maintained at a temperature of 265 ° C for 5 minutes, compressed with a cold section at 3 times and a temperature of i ^ d, and performed 2 minutes at a temperature of 40 ° C and a pressure of 15 MPa.于 表 U。 In Table U. [Table 10] arrived at Yuzhai Qizi.-一 ^ __ (Unit mass% Example 11 Comparative Example 12 PPS 15.1 15.1 Modified SEBS 3,78 3.78 Broken material A1 81.1 Carbon material A4 81.1 PPS: Polysulfide Ether, Susteel B385 modified SEBS manufactured by Tosoh Corporation: Modified stupid ethylene-ethylene_butene_styrene block copolymer, ceyton FG19 32 200540880 manufactured by cleyton Polymer Japan [Table 11] Early physical properties --- ----- Example 11 ------- Comparative Example 12 ------_ 4.2 8.7 jmQcn ^ 5.2 6.3 693 • ------___ 65.1 GPa --- 12.6 -------- ----- _ 13.2 1.0 " 一 -----, .MM-, Ι 0.68 12.3 78.5 Volume zero jg inflammation contact g resistance bending 彳 bending elasticity bending deflection almost = 1 among 'contains less butterflies, nitrogen and sulfur components The extraction method with hot water is excellent. The method of measuring the characteristics of the molded body is shown below. ≪ Volume resistivity > The measurement is performed by the four-probe method in accordance with JISK7194. ≪ Contact resistance > In the 2nd_four-probe method, measure 3 resistance values, and contact the carbon paper (TGP_H-060 manufactured by Toray) with the following formula: Resistance (Rc > octamer and a 'wrong by using test piece (imm), charcoal paper (20mmx20mmx (U9mm), gold-plated copper plate (20mmx20mmx〇5jnm), sandwiched with the carbon paper The test piece was further sandwiched between two gold-plated copper plates, and a uniform pressure of 2 MPa was applied. Between the gold-plated copper plates, a constant current of 1 A was flowed in the penetrating direction, and the resistance was calculated by measuring the voltage of the machine (&) .Similarly, 3 pieces of carbon paper are sandwiched by 2 pieces of gold-plated 33 200540880 copper plate, and the resistance ⑻ is also taken out by 2 pieces of gold-plated copper plate. Further borrow ⑻. From the above 3 'values, below 22; , Then determine the resistance and resistance value. And use the following formula to remove the connection between the carbon paper and the test piece.

Rc = (Ri + R2 ~ 2R3) xS / 2 Impedance calculated from measurement 1 (Ω) Impedance calculated from measurement 2 (Ω) Impedance calculated from measurement 3 (Ω)

Ri R2 r3 &lt; Bending strength, variable curvature elasticity, and bending distortion> Following the method of Augraph (AG4 ^ NI) made by T manufacturer f (shares), the method is to measure at intervals of 64mm and bending speed lmm / min. Strip U, two-point flexural strength measurement was performed on a test piece C80mm (&lt; 10mm x 1.5mm). Re-application Example 12 The composition of Example 1 was poured into a mold that can be made 200mmxl20mmxl 5rnm large, and a groove with a width of 1mm on both sides and a groove depth of 0, and a groove with a depth of 5 sides. I use a 3 = t compression molding machine to The mold was heated at a pressure of 180 ° C and a pressure of 50 ° C for 10 minutes and was heated under pressure to obtain a thin, thin flat plate for a battery. The flat volume of the obtained double-groove was 561ηΩαη, the contact resistance was 3.1mncm2, the thermal conductivity was 19w / m · κ, and the air permeability was 23 × 10-W / sec. iSMJ3 Pour the composition of Example 5 into a mold that can be made into a groove with a width of 1mm and a groove depth of 0.5mm on the double-sided forming groove: using a 380t compression molding machine, The mold temperature was 23 ° C. After heating under pressure of 0, 50 MPa for 3 minutes, the temperature was lowered to 135 ° C and held for 5 minutes. 34 200540880 Next, the temperature was lowered to 60C to obtain a molded body in the shape of a separator for a fuel cell. The obtained molding system was grooved on both sides, with a volume resistivity of 42 mQcm, a contact resistance of 2.8 mQcm2, a thermal conductivity of 2 iw / m · κ, and a ventilation rate of 4.6 × 10-9 cm2 / sec. The measurement method of the flat plate characteristics is shown below. &lt; Thermal conductivity &gt; A laser flash method (tw method, laser flash method for measuring thermal constant PEI, LF / TCMFA8510B manufactured by Rigaku Corporation) was used at a temperature of 80. 〇, ^ in the air, irradiated with ruby laser light (excitation voltage of 25kv), the measurement of ^ (diameter plOmm, thickness 1.7_) measurement. <Ventilation rate> The measurement was performed at 23 ° C in accordance with JISK7126A method using helium gas. [Effects of the Invention] The test result of the sassafras tree has the characteristics of excellent impurity-conducting and bending properties, and low electric conductivity. Therefore, the resin composition of the present invention,

It is especially suitable for fuel cell separators. 35 200540880 [Brief description of the drawings] Figures l (a) to (b) are schematic cross-sectional views showing the method for measuring the powder compaction resistivity (pressure direction). Fig. 2 is a schematic cross-sectional view showing a method for measuring contact resistance. Component symbol description:

1.1 '~ Voltage measurement terminal 2 ~ Sample 3 ~ Side frame 4 ~ Compression rod 5,5' ~ Copper electrode 6 ~ Voltage meter 7 ~ Constant current generating power source 8 ~ Carbon paper 9 ~ Test piece 10 ~ Gold-plated copper 11 ~ Constant current generator 12 ~ Voltmeter

36

Claims (1)

200540880 10. Scope of patent application: 1: a kind of conductive tree moon composition, containing: (A) the gas component is less than mass%, the 52 component is 0.005 mass% or less carbonaceous material containing stone pentene, and Resin adhesive. 2. The conductive resin composition according to item 1 of the patent application range, wherein (A) the boron in the boron-containing carbonaceous material is 0.01 to 5% by mass. ^ For the conductive resin composition according to item 1 or 2 of the scope of patent application, wherein (A) φ boron carbonaceous material has boron nitride (BN) of 0.5 mass% or less. 4. If the conductive resin composition of item 1 or 2 of the patent scope is requested, it contains: it) boron-containing carbonaceous material 20 to 99% by mass, and (B) resin adhesive 80 to 1 mass 10 / 〇 . ^ The conductive resin composition of item 1 or 2 of the applied patent scope, wherein the ratio of the amount of f of the carbonaceous material and pure water of (A) I stone is 5 to 5 at a temperature of 15 (rc, 120 hours). Under the conditions, the conductivity of the water extracted by hot water is 15G] LiS / em or less. ^ If applied, the conductive resin composition of item 1 or 2 of the patent, in which the negative material of ⑷2 ^ is under pressure. The compacted resistivity of the powder in the direction of pressure in the state of 1 MPa is less than 0.05 Qcm. ^ As for the conductive resin composition in the scope of patent application item 1 or 2, wherein (A) 3: of a carbonaceous material The raw material is one selected from the group consisting of coke, mesophase carbon, pitch, charcoal, resin charcoal, f, artificial graphite, expanded graphite, carbon black, carbon fiber, fumed carbon fiber, and stone. A combination of two or more types. 8. As described in the conductive resin composition of item 1 or 2 of the patent, wherein (B) 37 200540880 resin adhesive contains 0.5 ~ 80 «amount ° / ❶ elastomer component. 9 A conductive shaped body, which will be any one of the patent application scope 1 to $. Conductive tree The fat composition is formed. 10. For example, in the conductive molded body of item 9 of the patent application, the volume resistivity is less than 0.1Ωαη and the contact resistance is less than 0.1Qcm2. 11. A fuel cell isolation The membrane is made of a conductive shaped body such as the scope of application for patents No. 9 or 10. Lu I2 · The fuel cell separator membrane according to the scope of patent applications for No. 11 in which the width is formed on both sides of 0.1 ~ 2_, A trench with a depth of 0.1 to l.Smm, the thickness of the thinnest part is less than or equal to imm, the volume resistivity is less than or equal to 0.1Ωατι, and the contact voltage is less than or equal to q mcm2.