WO2003025069A1 - Composition elastomere thermoplastique - Google Patents

Composition elastomere thermoplastique Download PDF

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Publication number
WO2003025069A1
WO2003025069A1 PCT/JP2002/009523 JP0209523W WO03025069A1 WO 2003025069 A1 WO2003025069 A1 WO 2003025069A1 JP 0209523 W JP0209523 W JP 0209523W WO 03025069 A1 WO03025069 A1 WO 03025069A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic elastomer
elastomer composition
carbon fiber
filler
diameter
Prior art date
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PCT/JP2002/009523
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English (en)
Japanese (ja)
Inventor
Shinichi Toyosawa
Kunio Machida
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Bridgestone Corporation
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Publication date
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Publication of WO2003025069A1 publication Critical patent/WO2003025069A1/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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the present invention relates to a thermoplastic elastomer composition (hereinafter, also simply referred to as “composition”). More specifically, it has good heat conductivity, electric conductivity, mechanical properties, and the like, and has molding properties such as kneading properties.
  • the present invention relates to a thermoplastic elastomer composition having excellent heat resistance. 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 mixed in various ways, as well as the characteristics of the basic material itself as the base material.
  • power pump racks and silica are widely known as fillers for obtaining the reinforcing effect of natural rubber and various thermosetting synthetic rubbers, and alumina is used to enhance thermal conductivity.
  • alumina is used to enhance thermal conductivity.
  • electrical conductivity for example, boron nitride or the like, and a metal powder such as copper or nickel, or conductive carbon are 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, in particular, a thermoplastic elastomer composition. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a structure made of a carbon atom having a specific shape as a filler, a thermoplastic elastomer obtained by adding only a small amount is used.
  • the inventors have found that the thermal conductivity and mechanical properties of one composition are greatly improved, and that sufficient effects can be obtained without adversely affecting the other properties, thereby completing the present invention.
  • thermoplastic elastomer composition of the present invention comprises a thermoplastic elastomer material and a filler, and has at least a length of 0.1 to 50 ⁇ m and a diameter of 0 as the filler. It is characterized in that carbon fibers of 0.2 to 0.5 m are blended.
  • the compounding amount of the carbon fiber in the present invention is preferably 0.0001 to 20% by volume of the entire thermoplastic elastomer composition.
  • the thermoplastic elastomer composition of the present invention may contain at least one of the force pump rack and the inorganic filler in an amount of 1 to 40% by volume.
  • thermoplastic elastomer composition preferably has a JIS A hardness of 1 to 90.
  • the carbon fiber has a length of 0. ⁇ 30 ⁇ , hollow fibers with diameters of 2 to 60 nm, and fibers with a length of l to 50 iim and a diameter of 0.05 to 0.5 m produced by vapor phase growth are preferably used. be able to.
  • thermoplastic elastomer composition of the present invention comprises a thermoplastic elastomer as a base material and a carbon fiber having a specific structure as a filler.
  • carbon fiber with a specific structure as the filler it is possible to obtain sufficient effects such as thermal conductivity and mechanical properties by adding a small amount. It does not cause inconveniences such as deterioration of other properties and moldability due to the large amount of addition.
  • the thermoplastic elastomer used in the present invention is a material that exhibits the properties of an elastomer at normal temperature, and is plastically deformed by an external force at a high temperature so that injection molding is possible.
  • a styrene-based material, an olefin-based material examples include urethane-based, ester-based, amide-based, and fluorine-based block polymers, graft polymers, ionomers, and the like, and polymers having an appropriate degree of crystallinity, such as stereoblock polypropylene and 1,2-polybutadiene. be able to.
  • those having physical properties according to the 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 of 0.1 to 50 mm and a diameter of 0.002 to 0.5 m, and has a hollow structure. May also be solid.
  • carbon fibers so-called carbon nanotubes and so-called vapor-grown carbon fibers produced by vapor-phase growth can be preferably used.
  • 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 im ⁇ , length 100 m). the degree) of 1 0 - 3 times of the order one, has a very fine tubular structure.
  • carbon nanotubes have an aspect ratio on the order of 10 i to 10 3 , the tensile strength is extremely high, for example, about 45 GPa, and the appearance of a repeating structure of six-membered rings constituting a cylinder have any of the electrical properties of the metal properties and semiconductor-like characteristics by people, for example, the current density is much as compared 1 O MA / cm 2 in 1 G AZ cm 2 degree and superconductors It is said to have excellent mechanical and electrical properties, such as high values.
  • the carbon nanotube to be used preferably has a length of 0.1 to 30 Hm, particularly 0.1 to 10 m.If it is shorter than 0.1 lm, the length is too small. The effect of improving the characteristics according to the invention is difficult to exert, and if it exceeds 30 m, effective dispersion in the composition is obtained because the entanglement between carbon nanotubes becomes strong. Is not easy, and neither is preferable.
  • the diameter is preferably in the range of 2 to 60 nm, particularly preferably in the range of 2.5 to 50 nm.
  • 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 synthesized by a plasma CVD (chemical vapor deposition) method, a thermal CVD method, a surface decomposition method, a fluidized gas phase synthesis method, an arc discharge method, and the like. Those obtained by a gas phase synthesis method are particularly preferred.
  • 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 used as appropriate.
  • carbon nanotubes manufactured by Materials Technologies Research, Inc. of the United States (MTR (Materials, Technologies, Research; Ltd.) can be used. Can be used.
  • the vapor-grown carbon fibers is usually forces one carbon fiber one (CF) (mean diameter 5 [pi! ⁇ , Length 1 0 0 _tm about) 1 0 2 - :! of . - for one times the order one is a fine fibrous structure, rather difficulty arise problems such as dispersibility than the case of adding conventional carbon fiber one and achieve the same performance improvement There are advantages that can be.
  • 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. 5 ⁇ 0.5 ⁇ m, especially in the range of 0.1 ⁇ 0.4 4, average length :!
  • vapor grown carbon fiber VGCF registered trademark manufactured by Showa Denko KK can be used.
  • the compounding amount of the carbon fiber according to the present invention is 0.1% of the entire thermoplastic elastomer composition. It is preferably within a range of from 0.1 to 20% by volume, particularly preferably from 0.1 to 15% by volume. When the content is 0.01% by volume or more, the desired performance can be sufficiently obtained, and when the content is 20% by volume or less, the expected effect of improving the performance is sufficiently exhibited. In addition, it is possible to avoid a decrease in workability in mixing and molding.
  • the Young's modulus is preferably in the range of 1 to 100 MPa, particularly preferably in the range of 2 to 80 MPa.
  • the 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. it can.
  • the JISA hardness of the thermoplastic elastomer composition of the present invention is preferably in the range of 1 to 90.
  • thermoplastic elastomer composition of the present invention various reinforcing fillers (hereinafter, sometimes referred to as “other fillers”) such as carbon black, inorganic fillers, etc., in addition to the carbon fibers described above, may be used. They can be appropriately blended.
  • the content of the other filler is preferably not more than 60% by volume, particularly preferably not more than 40% by volume of the whole filler.
  • Suitable other fillers include carbon black, silica, and inorganic fillers described below.
  • carbon black includes channel black, furnace black, acetylene black, and thermal black.
  • Specific examples include SRF, GPF, FEF, HAF, IS AF, and SAF. it can. In the present invention, any of these can be used, but it is preferable to appropriately select and use the thermoplastic elastomer composition according to the use and blending thereof.
  • silica can be suitably used as the inorganic filler.
  • the silica used in the present invention is not particularly limited, and those conventionally used for reinforcing rubber, for example, dry-processed silica (gayic anhydride), wet-processed silica (hydrous silicate), calcium silicate, and silicate 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. Ma
  • colloidal characteristics and the like can be appropriately selected according to the purpose and use.
  • BET nitrogen adsorption specific surface area
  • inorganic fillers include the following general formula (I),
  • M 1 is selected from metals selected from the group consisting of aluminum, magnesium, titanium and calcium, oxides or hydroxides of these metals, and hydrates thereof.
  • M, x, y, and z are respectively integers from 1 to 5, integers from 0 to 10, integers from 2 to 5, and integers from 0 to 10). It is 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 (A 1 2 0 3 ⁇ H 2 0), Gibusai bets, aluminum hydroxide, etc. Baiyarai preparative [A 1 (OH) 3] , magnesium hydroxide [Mg (OH), magnesium oxide (MgO), talc (3 Mg_ ⁇ '4 S i 0 2' H 2 ⁇ ), ⁇ evening Parujai bets (5 Mg O '8 S i ⁇ 2' 9 H 2 0), titanium white (T i ⁇ 2), titanium down black (T i 0 2n - J, calcium oxide (C a O), calcium hydroxide [C a (OH) 2] , magnesium aluminum oxide (MgO 'A l 2 ⁇ 3), clay (A l 2 O - 2 S i 0 2), kaolin ( ⁇ 1 2 0 3 ⁇ 2 S i ⁇ 2 ⁇ 2 H 2 0), Pairofui La wells (A l 2 0 3 '4 S i 0
  • n is an integer of 0 to 3.
  • Ru include Monmori furnace bets like.
  • these other fillers may be used alone or in combination of two or more.
  • thermoplastic elastomer composition of the present invention in the case where a silicic acid or other inorganic filler is used, a coupling agent can be blended as required to further improve its 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-based coupling agent is particularly preferable.
  • examples of the silane coupling agent include the general formula (RO) 3 S i -S m-S i (OR) 3 or XS i (OR) 3 (where R is X is a functional group that reacts with an organic substance (eg, a mercaptoalkyl group, an aminoalkyl group, a vinyl group, an epoxy group, a glycidoxyalkyl group, a benzothiazolyl group). , N, N-dimethylcarbamoyl group, etc.), and m is an integer satisfying 0 ⁇ m ⁇ 9), specifically, bis (3-triethoxysilylpropyl).
  • R is X is a functional group that reacts with an organic substance (eg, a mercaptoalkyl group, an aminoalkyl group, a vinyl group, an epoxy group, a glycidoxyalkyl group, a benzothiazolyl group).
  • N N-dimethylcarbamoyl group, etc.
  • Tetrasulfide bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylethyl) tetrasulfide, Bis (3-triethoxysilylpropyl) disulphide, bis (3-trimethoxysilylpropyl) disulphide, bis (3-triethoxysilylpropyl) trisulphide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl Triethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 3-aminopropyl trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, r-glycidoxypropyltrimethyoxysilane, ⁇ -glycidoxy
  • such a coupling agent may be used alone, or two or more kinds may be used in combination. It is preferable that the compounding amount is 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 is less than 1 part by weight, the effect of the compounding may not be sufficiently exhibited. If the amount is more than 50% by weight, the effect is not improved in proportion to the amount, which is rather disadvantageous economically. In consideration of the mixing effect and the economical efficiency, the more preferable content of the coupling agent is in the range of 2% by weight to 40% by weight, particularly preferably 5% by weight to 30% by weight.
  • thermoplastic elastomer composition of the present invention has a low thermal conductivity by blending a small amount of the above-mentioned predetermined carbon fiber without significantly changing other physical properties and without impairing moldability. It can be widely used in electrical and electronic parts, tires, belts, and various other products because it can significantly improve properties such as electrical conductivity.
  • the thermoplastic elastomer composition of the present invention includes, in addition to the reinforcing filler described above, for example, an antioxidant, a lubricant, a surface treatment agent, a pigment, an ultraviolet absorber, an antistatic agent, a dispersant, A neutralizing agent, a foaming agent, a cross-linking agent, and the like can be appropriately used.
  • a method for mixing and molding the thermoplastic elastomer composition of the present invention a known method used for mixing and molding of various ordinary compositions can be used, and there is no particular limitation.
  • thermoplastic elastomer styrene ethylene propylene styrene block copolymer (SEPS) as a thermoplastic elastomer and polypropylene (P P) and various additives were mixed and kneaded with a roll at 150 ° C., and then a sheet of a thermoplastic elastomer composition having a thickness of 0.5 mm was produced by an electric heat press.
  • SEPS styrene ethylene propylene styrene block copolymer
  • P P polypropylene
  • Multilayer carbon nanotube (closed), tube diameter: 7 to 12 nm, tube length: 0.5 to 10 urn, tube layer: 5 to 50 layers, manufactured by MTR (Materials Technologies Research), U.S.A., ARC Made by the discharge method
  • the sheets of each of the obtained compositions were evaluated for their JISA hardness, fracture physical properties (rupture strength, elongation at break) and thermal properties (thermal conductivity, thermal resistance).
  • the JISA hardness is measured in accordance with JISK 6253-19997
  • the breaking strength and the elongation at break are measured in accordance with JISK625-1—1997
  • the thermal conductivity is measured in Kyoto.
  • the thermal resistance was measured using a rapid thermal conductivity meter QTM-500 manufactured by Electronics (II), and the thermal resistance was measured using a transistor radiator-type thermal resistance meter manufactured by Com Electronics Co., Ltd. The results are shown in Table 2 below.
  • thermoplastic elastomer composition of Example 1 containing about 1.1% by volume of carbon nanotubes had a good thermal conductivity. Compared to Comparative Example 1, which uses only alumina, the thermal conductivity is significantly improved.This is due to the comparison of Comparative Example 2 in which alumina was increased instead of carbon nanotubes. The difference between the two can be clearly seen. Furthermore, when compared with Comparative Example 3 in which the amount of alumina was greatly increased, the physical properties of the composition were reduced when a large amount of alumina was added, so that an effect of improving thermal conductivity equivalent to that of the carbon fiber used in the present invention was obtained. It turns out to be difficult. That is, the addition of carbon nanotubes improves the values of thermal conductivity and thermal resistance without adversely affecting the hardness and the crushing properties. It was confirmed that a performance improvement effect equal to or higher than that obtained by simply adding was obtained.
  • thermoplastic elastomer was changed to a styrene-butadiene-styrene triblock copolymer.
  • thermoplastic elastomer styrene-butadiene-styrene triblock copolymer (SBS) as a thermoplastic elastomer and various additives were mixed and rolled into a 150 roll. After kneading, a sheet of a thermoplastic elastomer composition having a thickness of 0.5 mm was produced by an electric heat press.
  • SBS styrene-butadiene-styrene triblock copolymer
  • SEPS styrene ethylene propylene styrene block copolymer
  • PP polypropylene
  • Table 5 The amounts in Table 5 below are all parts by weight.
  • VCF F TM Vapor-grown carbon fiber manufactured by Showa Denko KK (fiber diameter 0.15 im, fiber length 10 to 20 ⁇ m)
  • thermoplastic elastomer was changed to a styrene-butadiene-styrene triblock copolymer.
  • thermoplastic elastomer The styrene-butadiene-styrene triblock copolymer (SBS) as a thermoplastic elastomer was mixed with various additives in the composition shown in Table 7 below to form a roll at 150 ° C. After kneading, a sheet of a thermoplastic elastomer composition having a thickness of 0.5 mm was produced by an electric heat press. The amounts in Table 7 below all represent parts by weight. Table 7
  • SBS styrene-butadiene-styrene triblock copolymer
  • thermoplastic elastomer composition of the present invention by using a structure composed of a carbon atom having a specific shape as a filler, the hardness and the fracture can be improved even when a small amount is added. Significant improvements in properties such as thermal conductivity, thermal resistance, and electrical conductivity can be obtained without significantly changing other physical properties such as physical properties and without impairing moldability. Therefore, the thermoplastic elastomer composition of the present invention can be used not only widely in electric and electronic parts, tires, belts, and other various products, but also with little increase in hardness, while maintaining flexibility. Since a low thermal resistance value can be obtained, it is extremely effective when used for heat dissipation sheets.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition élastomère thermoplastique comprenant une matière élastomère thermoplastique et une charge, se caractérisant en ce que la charge comprend une fibre de carbone dont la longueur est comprise entre 0,1 et 50 νm et le diamètre, entre 0,002 et 0,5 νm. la fibre de carbone est de préférence une fibre creuse de longueur comprise entre 0,1 et 30 νm et de diamètre de l'ordre de 2 à 60 nm, c.-à-d. un nanotube de carbone ou une fibre préparée par croissance en phase vapeur et dont la longueur est comprise entre 1 et 50 νm et le diamètre, entre 0,05 et 0,5 νm, c.-à-d. la fibre de carbone obtenue par croissance en phase vapeur. La fibre de carbone représente de préférence entre 0,001 et 20 % en volume de la quantité totale de composition élastomère thermoplastique. Ladite composition élastomère thermoplastique est efficace en termes de conductivité thermique, de conductivité électrique, de résistance thermique, de caractéristiques mécaniques et similaires, et est également excellente en matière de moulabilité, telle que le malaxage.
PCT/JP2002/009523 2001-09-14 2002-09-17 Composition elastomere thermoplastique WO2003025069A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001/279986 2001-09-14
JP2001279986 2001-09-14
JP2001279985 2001-09-14
JP2001/279985 2001-09-14

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004229869A (ja) * 2003-01-30 2004-08-19 Mizuno Corp ゴルフクラブヘッド
JP2004351034A (ja) * 2003-05-30 2004-12-16 Kenji Onoda 高強度ゴルフボール
JP2006158950A (ja) * 2004-11-15 2006-06-22 Kasco Corp ゴルフボール
US7307120B2 (en) 2002-01-30 2007-12-11 Idemitsu Kosan Co., Ltd. Thermoplastic resin composition, polycarbonate resin composition, and molded article thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281905A (ja) * 1999-03-30 2000-10-10 Teijin Chem Ltd 電気抵抗の制御された炭素繊維含有熱可塑性樹脂組成物
JP2002038033A (ja) * 2000-05-19 2002-02-06 Suzuki Sogyo Co Ltd 熱伝導性シート
JP2002273741A (ja) * 2001-03-15 2002-09-25 Polymatech Co Ltd カーボンナノチューブ複合成形体及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281905A (ja) * 1999-03-30 2000-10-10 Teijin Chem Ltd 電気抵抗の制御された炭素繊維含有熱可塑性樹脂組成物
JP2002038033A (ja) * 2000-05-19 2002-02-06 Suzuki Sogyo Co Ltd 熱伝導性シート
JP2002273741A (ja) * 2001-03-15 2002-09-25 Polymatech Co Ltd カーボンナノチューブ複合成形体及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7307120B2 (en) 2002-01-30 2007-12-11 Idemitsu Kosan Co., Ltd. Thermoplastic resin composition, polycarbonate resin composition, and molded article thereof
US8044127B2 (en) 2002-01-30 2011-10-25 Idemitsu Kosan Co., Ltd. Thermoplastic resin composition, polycarbonate resin composition, and molded article thereof
JP2004229869A (ja) * 2003-01-30 2004-08-19 Mizuno Corp ゴルフクラブヘッド
JP2004351034A (ja) * 2003-05-30 2004-12-16 Kenji Onoda 高強度ゴルフボール
JP2006158950A (ja) * 2004-11-15 2006-06-22 Kasco Corp ゴルフボール

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