WO2003050181A1 - Composition d'elastomere - Google Patents

Composition d'elastomere Download PDF

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Publication number
WO2003050181A1
WO2003050181A1 PCT/JP2002/009522 JP0209522W WO03050181A1 WO 2003050181 A1 WO2003050181 A1 WO 2003050181A1 JP 0209522 W JP0209522 W JP 0209522W WO 03050181 A1 WO03050181 A1 WO 03050181A1
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WO
WIPO (PCT)
Prior art keywords
rubber
elastic
carbon
diameter
length
Prior art date
Application number
PCT/JP2002/009522
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English (en)
Japanese (ja)
Inventor
Shinichi Toyosawa
Kunio Machida
Original Assignee
Bridgestone Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corporation filed Critical Bridgestone Corporation
Publication of WO2003050181A1 publication Critical patent/WO2003050181A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements

Definitions

  • the present invention relates to an elastic composition (hereinafter, also simply referred to as a “composition”). More specifically, the composition has good heat conductivity, electric conductivity, mechanical properties, etc., and also has excellent moldability such as kneading properties. Elastic composition. Background art
  • thermoplastic elastomers based on elastic materials such as natural rubber, various thermosetting synthetic rubbers, and thermoplastic elastomers, depending on their characteristics. Tomato compositions have been used. The performance and functions of such products are greatly affected by the vulcanization conditions and other auxiliary materials such as fillers, which are variously blended, as well as the characteristics of the elastic material itself as the base material.
  • carbon black is widely known as a filler for obtaining a reinforcing effect of natural rubber and various thermosetting synthetic rubbers, and alumina is used for enhancing thermal conductivity.
  • a metal powder such as copper or nickel, or conductive carbon is mixed.
  • thermoplastic elastomers from those having mechanical properties close to vulcanized rubber to those having soft physical properties like gel, and various types of materials that can exhibit a wide range of physical properties. It has been expanded to applications. Even if such a thermoplastic elastomer is to be used for an application that requires a specific function, it is possible to achieve both the required performance and the characteristics as the elastomer by adding various fillers that perform the intended function. Is achieved.
  • an object of the present invention is to achieve various properties by using a filler that exhibits a high property improving effect only by adding a relatively small amount and does not adversely affect other performances such as mechanical properties.
  • An object of the present invention is to provide an elastic composition having physical properties with high productivity. Disclosure of the invention
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by using a structure made of carbon atoms having a specific shape as a filler, an elastic composition obtained only by adding a small amount
  • the present inventors have found that the thermal conductivity and mechanical properties of the material have been greatly improved, and that sufficient effects can be obtained without adversely affecting other physical properties, thereby completing the present invention.
  • the elastic composition of the present invention comprises a porous material and a filler, and the filler has at least a length of 0.1 to 50 m and a diameter of 0.002 to 0.5 m. Characterized in that carbon fiber and carbon black are blended.
  • the compounding amount of the carbon fiber in the present invention is preferably 0.001 to 20% by volume of the entire elastic body composition.
  • the compounding amount of carbon black is preferably 1 to 40% by volume of the whole elastic composition.
  • the elastic material may include a vulcanizable rubber, and in this case, preferably, the JIS hardness is 30 to 90.
  • the carbon fiber a hollow fiber having a length of 0.1 to 30 xm and a diameter of 2 to 60 nm, or a length of 1 to 50 ⁇ m, which is produced by a vapor phase growth method
  • Fibers having a diameter of 0.05 to 0.5 m can be suitably used.
  • the elastic body composition of the present invention comprises an elastic material as a base material and carbon fibers having a specific structure as a filler.
  • carbon fiber with a specific structure as a filler Therefore, the effect of improving thermal conductivity and mechanical properties can be sufficiently obtained only by adding a small amount, and other properties and moldability due to the large amount of addition are likely to occur when using conventional fillers. It does not cause inconvenience such as deterioration of the project.
  • the elastic material used in the present invention preferably contains at least one kind of thermosetting rubber (hereinafter sometimes referred to as “rubber material”), but may also contain a thermoplastic elastomer.
  • Rubber materials include natural rubber, general-purpose synthetic rubber, for example, emulsion-polymerized styrene rubber, solution-polymerized styrene-butadiene rubber, high cis-1,4 polybutadiene rubber, low cis-1,4 polybutadiene rubber, high cis-1,1, (4) Gen-based special rubber such as polyisoprene rubber, etc., for example nitrile rubber, hydrogenated nitrile rubber, black plain rubber, etc. Other special rubbers such as sulfonated polyethylene and the like, for example, hydrid rubber, fluoro rubber, polysulfide rubber, urethane rubber, silicone rubber and the like can be mentioned. From the viewpoint of the balance between cost and performance, natural rubber or general-purpose synthetic rubber is preferred.
  • Examples of the method of crosslinking the rubber material according to the present invention include a method of adding a zeolite, a peroxide, a metal oxide, and the like to crosslink by heating, a method of adding a photopolymerization initiator and crosslinking by irradiation with light, And a method of cross-linking by irradiation with radiation.
  • Thermoplastic elastomers exhibit the properties of elastomers at room temperature, and are plastically deformed by external force at high temperatures to enable injection molding. Examples of such materials include styrene-based, olefin-based, urethane-based and ester-based materials.
  • thermoplastic elastomers examples thereof include block polymers of amide type, amide type, fluorine type and the like, graft polymers, ionomers and the like, and polymers having an appropriate degree of crystallinity such as stereo block polypropylene and 1,2-polybutadiene.
  • those having physical properties according to the intended use can be appropriately used, and there is no particular limitation.
  • the carbon fiber used as the filler in the present invention preferably has a length in the range of 0.1 to 50 / m and a diameter of 0.002 to 0.5 m, and has a hollow structure. Or may be solid.
  • a so-called carbon nanotube or a so-called vapor-grown carbon fiber produced by a vapor-phase growth method is preferable. It can be used properly.
  • a carbon nanotube is a hollow structure composed of carbon atoms with a diameter of several nm to several tens of nm, and is made of ordinary carbon fiber (CF) (average diameter 5 n! 1 0 3 times on the order of about m), it has a very fine tubular structure.
  • Carbon nanotubes aspect ratio is 1 0 1 to 1 0 very high tensile strength to the order which is one of 3, for example, a 4 5 GP a degree, also by manifestations of the repeating structure of six-membered rings constituting the cylindrical have any of the electrical properties of the metal properties and semiconductor-like characteristics, for example, a much higher value as compared with 1 0 MAZ cm 2 of current density 1 G AZ cm 2 degree and superconductors It is said to have excellent mechanical and electrical properties.
  • the carbon nanotube to be used preferably has a length of 0.1 to 30111, particularly preferably 0.1 to 10 / im, and if shorter than 0.1 tm, it is too small to be used in the present invention. It becomes difficult to exhibit such a property improving effect, and if it exceeds 30 / zm, it becomes easy to obtain effective dispersion in the composition due to strong entanglement between the carbon nanotubes.
  • the diameter is preferably in the range of 2 to 60 nm, particularly preferably in the range of 2.5 to 50 nm. If the diameter is less than 2 nm, it is difficult to obtain an effective tube structure.If the diameter exceeds 60 nm, the aspect ratio does not increase, depending on the length. It is not preferable because the feature becomes difficult to appear.
  • the preferred aspect ratio of the carbon nanotube in the present invention is preferably in the range of 20 to 2000, more preferably in the range of 30 to 100.
  • Carbon nanotubes are preferably synthesized by plasma CVD (thermal chemical vapor deposition), thermal CVD, surface decomposition, fluidized gas phase synthesis, arc discharge, etc., especially for mass production. Those obtained by a fluidized gas phase synthesis method which is excellent in the above are particularly preferable.
  • Either single-walled nanotubes or multi-walled nanotubes can be used, and there are no particular restrictions on the number of tubes in a single-walled tube or the number of tube-walled tubes in a multi-walled tube.
  • commercially available carbon nanotubes can be appropriately used.
  • carbon nanotubes manufactured by Material Research Technologies, Inc. MMR (Materials, Technologies, Research) Ltd.
  • the vapor-grown carbon fibers is usually of carbon fiber (CF) (mean diameter 5 [pi! ⁇ , Length 1 0 0 / about zm) of 1 0 2 to 1 0 1 times the order of fine fibers Since it is a state-of-the-art structure, there is an advantage that problems such as dispersibility are less likely to occur than when ordinary carbon fiber is added, and a similar effect of improving performance can be obtained.
  • the vapor-grown carbon fiber is not particularly limited, and a fiber having a fiber diameter, a fiber length, and an aspect ratio according to required performance can be used as appropriate, and preferably, the average diameter is 0.0.
  • the compounding amount of the carbon fiber according to the present invention is preferably in the range of 0.001 to 20% by volume, particularly 0.1 to 15% by volume of the entire elastic composition.
  • carbon black In the elastic composition of the present invention, carbon black must be mixed together with the carbon fibers.
  • the carbon black includes channel black, furnace black, acetylene black, and thermal black depending on the production method, and specific examples include SRF, GPF, FEF, HAF, ISAF, and SAF. In the present invention, any of these can be used, but it is preferable to select and use them appropriately in accordance with the use and composition of the polymer composition. When a proper amount of carbon black is blended in the composition, a higher reinforcing effect can be obtained as compared with a case where only carbon fiber is blended.
  • the elastic composition of the present invention preferably has a Young's modulus in the range of 0.5 to 10 MPa.
  • Young's modulus is equal to or higher than the lower limit, a decrease in physical properties such as creep property and strength can be suppressed.
  • Young's modulus is equal to or lower than the upper limit, the elasticity of the composition can be sufficiently maintained.
  • the JISA hardness of the elastic composition of the present invention is preferably in the range of 30 to 90.
  • the elastic composition of the present invention may appropriately contain various inorganic fillers (hereinafter, also referred to as “other fillers”).
  • the content of other fillers is preferably not more than 60% by volume, particularly preferably not more than 40% by volume of the entire filler.
  • silica can be suitably used as the inorganic filler.
  • the silica used in the present invention is not particularly limited, and those which are conventionally used for reinforcing rubber, for example, dry silica (caie anhydride), wet silica (hydrated maleic acid), calcium gayate, and calcium acid It can be appropriately selected from aluminum and the like, and is preferably wet-process silica, which has the most remarkable effect of improving the fracture resistance.
  • the nitrogen adsorption specific surface area is in the range of 10 Om 2 / g to 300 m 2 / g.
  • the BET value is a value measured in accordance with ASTM D 4820-93 after drying at 300 for 1 hour.
  • inorganic fillers include the following general formula (I),
  • M 1 is a metal selected aluminum, magnesium, titanium and calcium or Ranaru group, oxides of these metals or Hydroxide, and at least one selected from hydrates thereof, wherein m, x, y, and z are integers of 1 to 5, integers of 0 to 10, and integers of 2 to 5, respectively. And an integer of 0 to 10) are preferably used.
  • Such an inorganic filler may further contain a metal such as potassium, sodium, iron, and magnesium, an element such as fluorine, and a group such as NH 4 .
  • alumina monohydrate (Alpha 1 2 ⁇ 3 ⁇ ⁇ 2 0), Gibusai bets, aluminum hydroxide, etc. Baiyarai preparative [A 1 ( ⁇ ) 3] , magnesium hydroxide [Mg (OH) J , magnesium oxide (Mg O), talc (3 M gO '4 S i 0 2' H 2 0), 7 evening Parujai bets (5 Mg O '8 S i ⁇ 2 - 9 H 2 0), titanium white (T i ⁇ 2), titanium down black (T i ⁇ 2n, calcium oxide (C A_ ⁇ ), calcium hydroxide [C a (OH) J, magnesium aluminum oxide (M g O 'A l 2 0 3), clay ( A l 2 0 - 2 S i 0 2) , kaolin ( ⁇ 1 2 0 3 ⁇ 2 S i O 2 ⁇ 2 H 2 0), Pairofui La wells (A l 2 0 3 '4 S i
  • M 1 is aluminum
  • Alumina is preferred, and aluminas and clays are particularly preferred.
  • Alumina is a compound represented by the following general formula (I) among the inorganic fillers represented by the above formula (I).
  • n is an integer of 0 to 3.
  • Clays include clay ( ⁇ 1 2 ⁇ 3 ⁇ 2 S i 0 2 ) and kaolin (A l 2 O
  • these other fillers may be used alone or in combination of two or more.
  • a coupling agent in the case of using a filler or other inorganic filler, a coupling agent can be added, if desired, in order to further improve the effect.
  • the coupling agent is not particularly limited, and any one of various conventionally known coupling agents can be selected and used. Among them, a silane coupling agent is particularly preferable.
  • examples of the silane coupling agent include the general formula (RO) 3 S i — Sm—S i (OR) 3 or XSI (OR) (where R is a group capable of hydrolyzing OR.
  • X is a functional group that reacts with an organic substance (eg, mercaptoalkyl group, aminoalkyl group, vinyl group, epoxy group, glycidoxyalkyl group, benzothiazolyl group, N, N —Dimethylcarbamoyl
  • m is an integer that satisfies 0 ⁇ m ⁇ 9), specifically, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3— Trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, bis (3—triethoxysilylethyl) tetrasulfide, bis (3—triethoxysilylprop
  • such a coupling agent may be used alone, or two or more kinds may be used in combination.
  • the amount is preferably selected in the range of 1% by weight to 50% by weight based on the total amount of the silica and the other inorganic filler. If the amount exceeds 50% by weight, the effect is not improved in proportion to the amount, but it is disadvantageous economically.
  • the content of the cutting agent is more preferably from 2% by weight to 40% by weight, particularly preferably from 5% by weight to 30% by weight.
  • the elastic body composition of the present invention has a reinforcing property by blending a small amount of the above-mentioned predetermined carbon fiber and carbon black without largely changing other physical properties and without impairing moldability. It can be widely used for electrical and electronic parts, tires, belts, and various other products, because it can greatly improve the properties such as thermal conductivity and electrical conductivity while maintaining sufficient properties.
  • the elastic composition of the present invention contains, in addition to the reinforcing filler described above, additives generally used in the rubber industry, such as a vulcanizing agent, a vulcanization accelerator, a crosslinking agent, an antioxidant, Normal rubber additives such as softeners, It can be used as appropriate.
  • Multi-layer carbon nanotube manufactured by MTR (Materials Technology Research), USA, tube diameter 7 to 12 nm, tube length 0.5 to 10 im, tube layer 5 to 50 layers Manufactured by ARC discharge method
  • Raboplus mill manufactured by Toyo Seiki Co., Ltd. was used to set NR at 70 at 50 rD. After mastication for 3 minutes at m, the additives shown in Table 1 above, except for the vulcanization accelerator and sulfur, were added, and the mixture was further mixed at 70 at 3 Orpm. The obtained mixture was taken out, cooled and weighed, then the remaining vulcanization accelerator and sulfur were added, and the mixture was mixed again at 50 rpm at 30 rpm using a brabender.
  • the kneaded mixture was vulcanized at 150 t ⁇ 15 minutes using a high-temperature press to produce a vulcanized rubber sheet having a thickness of 1 mm.
  • JISA hardness is measured in accordance with JISK 6 25 3-1 997
  • breaking strength and the breaking elongation are measured in accordance with JIS K 6 25 1-1 997
  • thermal conductivity is measured in Kyoto.
  • the measurement was performed using a rapid thermal conductivity meter QTM-500 manufactured by Electronics Co., Ltd. The results are shown in Table 2 below.
  • Example 1 As is evident from the results in Table 2 above, the elastic composition of Example 1 containing about 1.7% by volume of carbon nanotubes was more fragile than Comparative Example 1 using only carbon black. Although the thermal conductivity was greatly improved without adversely affecting the physical properties and hardness, in Comparative Example 2 where alumina was conventionally used to increase thermal conductivity instead of carbon nanotubes, However, even if the compounding amount is 9 times, the thermal conductivity has little effect of improving. Further, from Example 2 and Comparative Example 3, it can be seen that the same effect is obtained in a system in which a part of carbon black is replaced by alumina.
  • Styrene butadiene copolymer was used as a rubber material in the formulation shown in Table 3 below. The same experiments and evaluations as above were performed using rubber (SBR). Table 4 shows the results.
  • Multi-layer carbon nanotube (closed), manufactured by MTR (Materials Technologies Research), U.S.A., Tube diameter 7 ⁇ : 12nm, Tube length 0.5 ⁇ 10. Tube layer 5 ⁇ 50 layer, ARC discharge method Made in
  • Natural rubber as a rubber material and various additives were mixed according to the compounding contents shown in Table 5 below, and a sheet of a vulcanized rubber composition was prepared according to the kneading conditions and sheet preparation conditions shown below. .
  • the amounts in Table 5 below all indicate parts by weight.
  • VCF® Vapor-grown carbon fiber manufactured by Showa Denko KK (fiber diameter 0.15 ⁇ m, fiber length 10 to 20 m)
  • Example 5 As is evident from the results in Table 6 above, the elastic composition of Example 5 containing about 2.1% by volume of the vapor-grown carbon fiber showed a comparative example using only carbon black. Thermal conductivity has been greatly improved without adversely affecting fracture properties and hardness, but alumina, which has been conventionally used to increase thermal conductivity instead of blending vapor grown carbon fibers In Comparative Example 8, where the blending amount was 7 times that of the vapor-grown carbon fiber, the effect of improving the thermal conductivity was insignificant, but other physical properties were affected. Further, from Example 6 and Comparative Example 9, it can be seen that the same effect can be obtained in a system in which a part of the carbon black is replaced with alumina. (Examples 7 and 8 and Comparative Examples 10 to: L 2)
  • SBR styrene-butadiene copolymer rubber
  • VCF F Vapor-grown carbon fiber manufactured by Showa Denko KK (fiber diameter 0.5 ⁇ m, fiber length 10 to 20 m)
  • the elastic composition of the present invention by using a structure made of a carbon atom having a specific shape as a filler, the hardness, the fracture properties, and the like can be obtained even when a small amount is added. Without significantly changing other physical properties and without impairing the moldability, it is possible to obtain a significant improvement in properties such as thermal conductivity, thermal resistance, and electrical conductivity. Therefore, the elastic composition of the present invention can be widely used for electric and electronic parts, tires, belts, and other various products. In particular, when it is necessary to vulcanize a large article or a thick article, the variation in vulcanization inside the article can be suppressed, and a homogeneous article can be provided.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une composition d'élastomère comprenant un matériau élastique et un composant de charge, ce dernier comprenant des fibres de carbone ayant une longueur de 0,1 à 50 νm et un diamètre de 0,002 à 0,5 νm, et du noir de carbone. On utilise de façon appropriée, comme fibres de carbone, des fibres creuses d'une longueur de 0,1 à 30 νm et d'un diamètre de 2 à 60 nm, à savoir des fibres dites nanotubes de carbone, les fibres étant préparées par croissance en phase vapeur et ayant une longueur de 1 à 50 νm et un diamètre de 0,05 à 0,5 νm, à savoir des fibres de carbone dites de croissance en phase vapeur. De telles fibres de carbone sont de préférence mélangées à raison de 0,001 à 20 % en volume, par rapport à la composition totale en élastomère. La composition d'élastomère présente des bonnes propriétés de conductivité thermique, de conductivité électrique, de résistance à chaud, de bonnes caractéristiques mécaniques et analogues, ainsi qu'une formabilité excellente, par exemple, une bonne aptitude au mélange.
PCT/JP2002/009522 2001-09-14 2002-09-17 Composition d'elastomere WO2003050181A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-279984 2001-09-14
JP2001279983 2001-09-14
JP2001279984 2001-09-14
JP2001-279983 2001-09-14

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005068386A (ja) * 2003-08-28 2005-03-17 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、並びに炭素繊維複合成形品及びその製造方法
JP2005082640A (ja) * 2003-09-05 2005-03-31 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、並びに炭素繊維複合成形品
JP2005179120A (ja) * 2003-12-19 2005-07-07 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、炭素繊維複合金属材料及びその製造方法
US7501459B2 (en) 2004-05-21 2009-03-10 Nissin Kogyo Co., Ltd. Carbon fiber composite material and method of producing the same
US7785701B2 (en) 2003-04-09 2010-08-31 Nissin Kogyo Co., Ltd. Carbon fiber composite material and process for producing the same
US8253318B2 (en) 2004-11-22 2012-08-28 Nissin Kogyo Co., Ltd. Method of manufacturing thin film, substrate having thin film, electron emission material, method of manufacturing electron emission material, and electron emission device
WO2021133407A1 (fr) * 2019-12-27 2021-07-01 Compagnie Generale Des Etablissements Michelin Mélange de caoutchouc à noir d'acétylène de surface spécifique élevée et de structure élevée

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JPH01289843A (ja) * 1988-05-16 1989-11-21 Asahi Chem Ind Co Ltd タイヤ用ゴム組成物
JPH02212370A (ja) * 1988-09-02 1990-08-23 Nikkiso Co Ltd 複合材料
JPH02228340A (ja) * 1989-03-01 1990-09-11 Asahi Chem Ind Co Ltd 感圧導電ゴム組成物
WO1990012842A1 (fr) * 1989-04-19 1990-11-01 Japan Synthetic Rubber Company, Ltd. Composes elastomeres thermoplastiques
JPH02302452A (ja) * 1989-05-17 1990-12-14 Morinobu Endo ゴム組成物
JPH06122785A (ja) * 1991-12-10 1994-05-06 Nikkiso Co Ltd 導電性組成物、導電性塗料、導電性インク及び電気回路基板
JPH08127674A (ja) * 1994-09-05 1996-05-21 Nikkiso Co Ltd 帯電防止性ゴム組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01287151A (ja) * 1988-05-13 1989-11-17 Asahi Chem Ind Co Ltd ゴム組成物
JPH01289843A (ja) * 1988-05-16 1989-11-21 Asahi Chem Ind Co Ltd タイヤ用ゴム組成物
JPH02212370A (ja) * 1988-09-02 1990-08-23 Nikkiso Co Ltd 複合材料
JPH02228340A (ja) * 1989-03-01 1990-09-11 Asahi Chem Ind Co Ltd 感圧導電ゴム組成物
WO1990012842A1 (fr) * 1989-04-19 1990-11-01 Japan Synthetic Rubber Company, Ltd. Composes elastomeres thermoplastiques
JPH02302452A (ja) * 1989-05-17 1990-12-14 Morinobu Endo ゴム組成物
JPH06122785A (ja) * 1991-12-10 1994-05-06 Nikkiso Co Ltd 導電性組成物、導電性塗料、導電性インク及び電気回路基板
JPH08127674A (ja) * 1994-09-05 1996-05-21 Nikkiso Co Ltd 帯電防止性ゴム組成物

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7785701B2 (en) 2003-04-09 2010-08-31 Nissin Kogyo Co., Ltd. Carbon fiber composite material and process for producing the same
US7927692B2 (en) 2003-04-09 2011-04-19 Nissin Kogyo Co., Ltd. Carbon fiber composite material and process for producing the same
US8808605B2 (en) 2003-04-09 2014-08-19 Nissin Kogyo Co., Ltd. Carbon fiber composite material and process for producing the same
JP2005068386A (ja) * 2003-08-28 2005-03-17 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、並びに炭素繊維複合成形品及びその製造方法
JP2005082640A (ja) * 2003-09-05 2005-03-31 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、並びに炭素繊維複合成形品
JP2005179120A (ja) * 2003-12-19 2005-07-07 Nissin Kogyo Co Ltd 炭素繊維複合材料及びその製造方法、炭素繊維複合金属材料及びその製造方法
US7501459B2 (en) 2004-05-21 2009-03-10 Nissin Kogyo Co., Ltd. Carbon fiber composite material and method of producing the same
US8253318B2 (en) 2004-11-22 2012-08-28 Nissin Kogyo Co., Ltd. Method of manufacturing thin film, substrate having thin film, electron emission material, method of manufacturing electron emission material, and electron emission device
WO2021133407A1 (fr) * 2019-12-27 2021-07-01 Compagnie Generale Des Etablissements Michelin Mélange de caoutchouc à noir d'acétylène de surface spécifique élevée et de structure élevée

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