WO2016200046A1 - Composite conducteur à conductivité améliorée et son procédé de fabrication - Google Patents

Composite conducteur à conductivité améliorée et son procédé de fabrication Download PDF

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Publication number
WO2016200046A1
WO2016200046A1 PCT/KR2016/004348 KR2016004348W WO2016200046A1 WO 2016200046 A1 WO2016200046 A1 WO 2016200046A1 KR 2016004348 W KR2016004348 W KR 2016004348W WO 2016200046 A1 WO2016200046 A1 WO 2016200046A1
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Prior art keywords
conductive composite
compound
conductivity
carbon nanotubes
phosphite
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PCT/KR2016/004348
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English (en)
Korean (ko)
Inventor
장형식
강경연
이승용
김성진
우지희
조동현
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주식회사 엘지화학
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Priority to CN201680001512.7A priority Critical patent/CN107075262B/zh
Publication of WO2016200046A1 publication Critical patent/WO2016200046A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a conductive composite composition, and more particularly to a conductive composite having a good conductivity and a method of manufacturing the same.
  • Thermoplastic resins are used in various applications.
  • polyamide resins and polyester resins have excellent balance between mechanical properties and toughness, they are used in various electric / electronic parts, mechanical parts, and automobile parts mainly for injection molding.
  • Butylene terephthalate and polyethylene terephthalate are widely used as materials for industrial molded products such as connectors, relays and switches in automobiles and electrical / electronic devices because of their excellent moldability, heat resistance, mechanical properties and chemical resistance.
  • non-crystalline resins such as polycarbonate resins are excellent in transparency and dimensional stability, and are used in various fields including various optical materials, electric devices, OA devices, and automobile parts.
  • antistatic properties such as antistatic and dust pollution prevention are required in order to prevent malfunctions and contamination of parts
  • electrical conductivity is required in the existing physical properties such as conductivity is required in automobile fuel pump parts. ) Is additionally required.
  • conductive carbon black is commonly used as a material for imparting conductivity to the resin
  • a large amount of carbon black needs to be added to achieve high electrical conductivity, and the structure of the carbon black may be decomposed during melt mixing. As a result, the workability of resin deteriorates, and also the problem that thermal stability and physical property fall remarkably is caused.
  • the problem to be solved by the present invention is to provide a conductive composite with improved conductivity.
  • Another object of the present invention is to provide a manufacturing method for producing a conductive composite having excellent conductivity.
  • the present invention to solve the above problems,
  • the conductivity improving additive is the conductivity improving additive
  • a conductive composite having at least two selected from phenolic compounds, phosphite compounds and polyalkylene wax compounds.
  • the phenolic compound may be a compound represented by the following formula (1).
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms containing an ester group
  • R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the phosphite compound may be a compound represented by the following formula (2).
  • R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • polyalkylene wax compound may be a polyethylene wax.
  • Phenolic compounds and phosphite compounds Phenolic compounds and phosphite compounds
  • Phosphite compounds and polyalkylene wax compounds are Phosphite compounds and polyalkylene wax compounds.
  • It may contain a phenolic compound and a polyalkylene wax compound.
  • the surface resistance of the conductive composite is 1.0 x 10 11 ⁇ / sq. It may be:
  • the additive for improving conductivity may be included in 1 to 30 parts by weight based on 100 parts by weight of carbon nanotubes.
  • the carbon nanotubes may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic polymer.
  • the average length of the carbon nanotubes is 1 ⁇ m to 1,000 ⁇ m, the purity may be 85% or more.
  • the present invention also includes a conductive polymer comprising melt kneading and extruding a thermoplastic polymer, a carbon nanotube, and an additive for improving conductivity comprising at least two selected from phenolic, phosphite and polyalkylene wax compounds. It provides a method for producing a composite.
  • the conductive composite according to the present invention includes at least two types of conductivity improving additives selected from phenolic, phosphite, and polyalkylene wax compounds, thereby maintaining the basic physical properties of the thermoplastic polymer resin used in the conductive composite. Since the surface resistance of the conductive composite can be reduced, it is possible to provide a conductive composite having excellent conductivity.
  • thermoplastic polymer Carbon nanotubes; And a phenolic compound, a phosphite compound, a polyalkylene wax compound, and a conductive composite including two or more kinds of additives for improving conductivity.
  • the phenolic, phosphite, and polyalkylene wax compounds when added alone, they do not affect the surface resistance of the composite material, but they are thermoplastic when two or more kinds or all three kinds are added. It was found that the surface resistance can be reduced while maintaining the basic physical properties of the polymer resin, thereby obtaining a conductive composite having significantly improved conductivity.
  • the mixing ratio of each combination is optimized through experiments.
  • the present invention by including the additive for improving the conductivity, while maintaining or improving the inherent mechanical properties and physical properties of the thermoplastic polymer used, it is possible to significantly reduce the surface resistance of the prepared conductive composite, excellent conductivity properties It is possible to provide a conductive composite having a, it is possible to predict the change in surface resistance according to the content, it is possible to more efficiently produce a conductive composite having an improved conductivity.
  • the thermoplastic polymer preferably has a measured relative viscosity of 1.5 to 5, more preferably 2 to 4.5, measured at a concentration of 1 g / dl at 25 ° C.
  • the relative viscosity is less than 1.5, since the viscosity is low, processing after melt kneading becomes difficult, and it may be difficult to obtain desirable physical properties.
  • the fluidity at the time of forming processing is bad because of high viscosity, and it may be difficult to make a molded article because sufficient injection pressure is not applied.
  • thermoplastic polymer according to the present invention preferably has a melt index of 0.5 to 100 g / min, more preferably 1.0 to 80 g / min, and when the melt index is less than 0.5 g / min, high shear force is required for melting. If kneading is difficult, carbon nanotubes are not dispersed well in the thermoplastic polymer, and the melt index exceeds 100 g / min, the impact strength of the molding may be seriously lowered.
  • thermoplastic polymer that can be used in the conductive composite
  • the thermoplastic polymer may be used without limitation as long as it is used as a thermoplastic polymer in the related art, and for example, polycarbonate resin, aramid resin, aromatic polyester resin, polyolefin resin, polyester Carbonate resin, polyphenylene oxide resin, polysulfone resin, polyethersulfone resin, polyarylene resin, cycloolefin resin, polyetherimide resin, polyacetal resin, polyvinyl acetal resin, polyketone resin, polyether ketone resin Polyether ether ketone resins, polyaryl ketone resins, polyether nitrile resins, polybenzimidazole resins, polyparabanic acid resins, polyamide resins; Vinyl-based polymers or copolymer resins obtained by polymerizing or copolymerizing at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds; Dien
  • polystyrene resins examples include, but are not limited to, polypropylene, polyethylene, polybutylene, and poly (4-methyl-1-pentene), and combinations thereof.
  • the polyolefin may be a polypropylene homopolymer (e.g., atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene), polypropylene copolymer (e.g., Polypropylene random copolymers), and mixtures thereof.
  • Suitable polypropylene copolymers include, but are not limited to, the presence of comonomers selected from the group consisting of ethylene, but-1-ene (ie 1-butene), and hex-1-ene (ie 1-hexene). Random copolymers prepared from the polymerization of propylene under. In such polypropylene random copolymers, comonomers may be present in any suitable amount, but typically in amounts of about 10 wt% or less (eg, about 1 to about 7 wt%, or about 1 to about 4.5 wt%) May exist.
  • polyester resin the homopolyester and copolyester which are polycondensates of a dicarboxylic acid component skeleton and a diol component skeleton are mentioned.
  • the homo polyester for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene diphenylate Etc. are typical.
  • polyethylene terephthalate is inexpensive, it can be used for a very wide range of applications, which is preferable.
  • the said copolyester is defined as the polycondensate which consists of at least 3 or more components chosen from the component which has a dicarboxylic acid skeleton and the component which have a diol skeleton which are illustrated next.
  • Examples of the component having a dicarboxylic acid skeleton include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ' -Diphenyl dicarboxylic acid, 4,4'- diphenyl sulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid, ester derivatives thereof, and the like.
  • Examples of the component having a glycol skeleton include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis ( 4 '-(beta) -hydroxyethoxyphenyl) propane, isosorbate, 1, 4- cyclohexane dimethanol, spiroglycol, etc. are mentioned.
  • the polycarbonate resin may be prepared by reacting diphenols with phosgene, halogen formate, carbonate ester or a combination thereof.
  • diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also called 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether and
  • the polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.
  • the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.
  • group polycarbonate resin etc. are mentioned as said linear polycarbonate resin.
  • the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates.
  • the polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin.
  • said polyester carbonate copolymer resin what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used.
  • cycloolefin type polymer a norbornene type polymer, a monocyclic cyclic olefin type polymer, a cyclic conjugated diene type polymer, a vinyl alicyclic hydrocarbon polymer, and these hydrides are mentioned.
  • Specific examples thereof include Apel (ethylene-cycloolefin copolymer manufactured by Mitsui Chemical Co., Ltd.), aton (norbornene-based polymer manufactured by JSR Corporation), zeonoa (norbornene-based polymer manufactured by Nippon Xeon Corporation), and the like.
  • the polyphenylene oxide resin is also referred to as polyphenylene ether, and has a structure in which -O- is bonded to a phenylene group as a repeating unit.
  • the phenylene group may have various substituents, for example, methyl group, ethyl group, halogen group, hydroxy group and the like.
  • nylon resin nylon resin, nylon copolymer resin and mixtures thereof can be used.
  • nylon resin Polyamide-6 (nylon 6) obtained by ring-opening-polymerizing lactams, such as well known epsilon caprolactam and ⁇ -dodecaractam; Nylon polymers obtainable from amino acids such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; Ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine , Metaxylenediamine, paraxylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1-amino-3-
  • Aliphatic, cycloaliphatic or aromatic diamines and aliphatic, cycloaliphatic or aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, terephthalic acid, 2-chloroterephthalic acid and 2-methylterephthalic acid
  • Nylon polymers obtainable from the polymerization of; Copolymers or mixtures thereof can be used.
  • nylon copolymer a copolymer of polycaprolactam (nylon 6) and polyhexamethylene sebacamide (nylon 6,10), a copolymer of polycaprolactam (nylon 6) and polyhexamethyleneadipamide (nylon 66), And copolymers of polycaprolactam (nylon 6) and polylauryllactam (nylon 12).
  • the carbon nanotube is a material in which carbon atoms arranged in a hexagonal shape in a tube form have a diameter of about 1 to 100 nm. Carbon nanotubes exhibit non-conductor, conductor or semiconducting properties depending on their unique chirality, and the carbon atoms are connected by strong covalent bonds, so that their tensile strength is about 100 times larger than steel, and they have excellent flexibility and elasticity. It is also chemically stable.
  • the type of carbon nanotubes that can be used in the conductive composite according to the present invention includes a single-walled carbon nanotube (SWCNT) composed of one layer and having a diameter of about 1 nm.
  • 'bundle' refers to a bundle or rope form in which a plurality of carbon nanotubes are arranged or intertwined side by side, unless otherwise stated, and also referred to as 'non-bundle'.
  • a non bundle or entangled type means a shape without a constant shape, such as a bundle or rope shape.
  • Such bundle-type carbon nanotubes basically have a shape in which a plurality of carbon nanotube strands are gathered together to form a bundle, and the plurality of strands may have a straight, curved or mixed form.
  • the bundle of carbon nanotubes may also have a linear, curved or mixed form thereof.
  • such a bundle of carbon nanotubes may have a thickness of 50nm to 100 ⁇ m.
  • the average diameter of the carbon nanotube strands for example, it can be used 1nm to 40nm.
  • the carbon nanotubes used as raw materials may have an average length of about 1 ⁇ m or more, for example, 1 ⁇ m to 10,000 ⁇ m, or 5 ⁇ m to 1,000 ⁇ m, or 10 ⁇ m to 300 ⁇ m. And, the thickness may have a range of 10nm to 1,000 ⁇ m. Bundle-shaped carbon nanotubes having an average length and thickness in this range may be more advantageous for improving the conductivity of the thermoplastic polymer-containing composite.
  • the carbon nanotubes have a network structure in the matrix of the thermoplastic polymer-containing conductive composite, and long carbon nanotubes are more advantageous in forming such a network, and as a result, the frequency of contact between the networks decreases, so that the carbon nanotubes have a network structure.
  • the resistance value can be reduced to increase the conductivity of the conductive composite.
  • the average length of the carbon nanotube remaining in the thermoplastic resin-containing composite material may be 100nm or more, preferably 100nm to 30 ⁇ m, or may have a range of 1 ⁇ m to 10 ⁇ m.
  • the average length of the carbon nanotubes may be measured by scanning electron microscope (SEM) or transmission electron microscope (TEM). That is, after obtaining a photograph of powdered carbon nanotubes as raw materials through these measuring devices, the average length was analyzed by an image analyzer, for example, Scandium 5.1 (Olympus soft Imaging Solutions GmbH, Germany). You can get it.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the carbon nanotubes used in the preparation of the thermoplastic polymer-containing composite have a relatively high bulk density, which may be more advantageous for improving the conductivity of the composite.
  • the bulk density of the carbon nanotubes may be 1 to 1,000 kg / m 3 , for example, it may have a range of 10 to 250 kg / m 3 , preferably 15 to 100 kg / m 3 .
  • the term "bulk density” means the apparent density of the carbon nanotubes in the raw material state, and can be expressed as a value obtained by dividing the weight of the carbon nanotubes by volume.
  • the resin solids may be organic solvents such as acetone, ethanol, n-hexane, chloroform, p-xylene, 1-butanol, petroleum ether, 1,2,4
  • the resultant measured by SEM or TEM using this dispersion can be analyzed using the image analyzer to obtain an average length and distribution state.
  • the carbon nanotubes may be used in an amount of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, and more preferably 2 to 5 parts by weight based on 100 parts by weight of the heat resistant thermoplastic polymer. have.
  • the content of the carbon nanotube is less than 0.5 parts, the surface resistance value of the composite material may be high, so that electrical properties may be deteriorated.
  • the carbon nanotube content is more than 10 parts by weight, the mechanical properties of the manufactured composite material may be reduced.
  • the carbon nanotubes may be preferably at least 85% pure.
  • the conductivity improving additive used in the conductive composite material according to the present invention may not only improve the surface resistance of the conductive composite, but may also have properties of improving the flowability of the resin, preventing oxidation and deterioration of physical properties due to high temperature.
  • the phenolic compound may be, for example, 2,6-di-tert-butylphenol (hereinafter abbreviated as tert-butyl)-2,6-di-t-butyl-p-cresol , 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylene Bis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-bis (2-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidene Bis (3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-buty
  • the compound represented by Formula 1 may be preferable.
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms containing an ester group
  • R 2 and R 3 are each independently a hydrogen atom, a straight or branched chain alkyl group having 1 to 6 carbon atoms.
  • At least one of R 2 and R 3 is preferably an alkyl group having 1 to 6 carbon atoms, and it is preferable that both R 2 and R 3 are branched alkyl groups.
  • the branched alkyl group is a hindered phenol compound adjacent to the phenol group.
  • phosphite compound examples include tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6- Hexamethylene-bis (N-hydroxyethyl-N-methylsemicacarbazide) -diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'- t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio ( 2'-Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-sal
  • At least one PO bond is bonded to an aromatic group, and specific examples thereof include tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) penta Erythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl -Di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecy
  • a compound represented by Formula 2 may be preferable.
  • R 4 and R 5 are each independently a hydrogen atom, a straight or branched chain alkyl group having 1 to 6 carbon atoms.
  • At least one of R 4 and R 5 is preferably an alkyl group having 1 to 6 carbon atoms, and it is preferable that both R 4 and R 5 are branched alkyl groups.
  • the polyalkylene wax compound preferably has a number average molecular weight (Mn) in the range of 300 to 30,000.
  • Mn number average molecular weight
  • oxidized polypropylene waxes, and oxidized ethylene propylene copolymer waxes are also included. Also included may be acid modified polyolefin waxes or polyolefin waxes modified with aromatic monomers.
  • the conductivity improving additive may be included in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of carbon nanotubes, preferably 1 to 20 parts by weight, more preferably 10 to 20 parts by weight, and less than 0.5 parts by weight. In the amount, the conductivity improvement effect of the conductive composite may not be obtained, and in an amount greater than 30 parts by weight, the mechanical properties of the conductive composite may be reduced.
  • the conductive composite is a flame retardant, flame retardant, lubricant, plasticizer, heat stabilizer, anti-drip agent, antioxidant, compatibilizer, light stabilizer, pigment, dye, inorganic additives and drip inhibitors, as long as it does not affect conductivity and physical properties. It may further include an additive selected from the group consisting of, the content may be used in an amount of 5 parts by weight or less based on 100 parts by weight of the carbon nanotubes. Specific kinds of these additives are well known in the art, and examples which can be used in the composition of the present invention may be appropriately selected by those skilled in the art.
  • the conductive composite according to the present invention may be manufactured through a extrusion process, and in general, an extrusion process is a molding method of supplying a raw material to an extruder to push it out of a structure of a heating cylinder to convert it into a continuous body having a predetermined cross section.
  • the raw material of the conductive composite supplied to the extruder is heated, softened and melted in the cylinder and transported while being kneaded and compressed by the rotation of the screw.
  • the flow of the raw material into a uniform melt is continuously extruded to the outside from the opening of the mold made into a desired shape and then cooled to obtain an extrusion result.
  • the raw material may have a different physical property through a kneading process subjected to mechanical pressure in a heated state.
  • a kneading process subjected to mechanical pressure in a heated state.
  • mechanical cutting occurs, so that the carbon nanotube remaining in the extrusion resultant May have a different shape from the carbon nanotubes supplied as a raw material. Therefore, it is preferable to proceed with the extrusion process while maintaining the physical properties of the raw material, it is necessary to properly control the extrusion conditions of the extruder.
  • the shape of the extruder is not limited, but may be classified into a single screw extruder having a single screw or a multi screw extruder having a plurality of screws, wherein the multi screw extruder has two screws for uniform kneading of additives.
  • a twin screw extruder can be illustrated.
  • the screw of the twin screw extruder is not particularly limited, and a screw such as a fully engaged type, an incompletely engaged type or a non-engaged type may be used. From the standpoint of kneading and reactivity, a fully engaged screw is preferred.
  • the screw may be rotated in the same direction or in the opposite direction, but is preferably rotated from the viewpoint of kneading property and reactivity. Most preferably, the screw is co-rotating and fully engaged.
  • the resin in the extrusion process in order to suppress the thermal deterioration of the resin in the extrusion process it can be melt kneaded by introducing an inert gas from the raw material inlet, nitrogen may be exemplified as the inert gas at this time.
  • a method of kneading a thermoplastic resin and a carbon nanotube in a batch, a resin composition (master pellet) containing carbon nanotubes in a high concentration in the thermoplastic resin is prepared, and then a prescribed concentration
  • the resin composition, the method of melt-kneading by adding a carbon nanotube (master pellet method), etc. can be illustrated so that it may become, and what kneading method may be used.
  • a method of melt kneading by introducing a thermoplastic resin from the extruder side and feeding the carbon nanotubes to the extruder using a side feeder can be exemplified.
  • the surface resistance of the conductive composite prepared according to one embodiment of the present invention 1.0 x 10 11 ⁇ / sq. It may be less than, preferably 1.0 x 10 9 ⁇ / sq. Or less, and more preferably 1.0 x 10 8 ⁇ / sq. It may be:
  • thermoplastic polymer, carbon nanotube and conductivity improving additive to the twin screw extruder with the content as shown in Table 1, raise the temperature profile to 280 °C, screw rotation speed 350rpm, feeder speed 24rpm, pelletizer 90 ⁇ 110rpm
  • the mixture was melt extruded under conditions to prepare a conductive composite pellet.
  • the total extrusion time required was about 8 minutes 30 seconds, and the amount prepared for the initial 1 minute 30 seconds was removed, and then the amount prepared for 6 minutes 30 seconds was obtained to obtain pellets in an amount of about 1.3 kg.
  • the surface resistance was measured using a four-point probe measurement method for five samples and then used the average value.
  • the resistance of each sample length was divided by length after measuring resistance value using two probes with 5 sample ends having a certain length.
  • ⁇ R is a value defined as follows.
  • X is the surface resistance ( ⁇ / sq.) Of the conductive composite to which the additive for improving conductivity is added.
  • Y is the surface resistance ( ⁇ / sq.) Of the conductive composite to which no additive for improving conductivity is added.
  • the conductive composite according to the present invention includes at least two types of conductivity improving additives selected from phenolic, phosphite, and polyalkylene wax compounds, thereby maintaining the basic physical properties of the thermoplastic polymer resin used in the conductive composite. Since the surface resistance of the conductive composite can be reduced, it is possible to provide a conductive composite having excellent conductivity.

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Abstract

La présente invention concerne un composite conducteur comprenant : un polymère thermoplastique ; des nanotubes de carbone ; et un additif améliorant la conductivité, l'additif améliorant la conductivité comprenant au moins deux éléments choisis parmi un composé à base de phénol, un composé à base de phosphate, et un composé cire à base de polyalkylène. Il est ainsi possible de produire un composite conducteur possédant une conductivité remarquablement améliorée par réduction de la résistance surfacique tout en maintenant les propriétés physiques de base d'une résine polymère thermoplastique.
PCT/KR2016/004348 2015-06-09 2016-04-26 Composite conducteur à conductivité améliorée et son procédé de fabrication WO2016200046A1 (fr)

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KR101999949B1 (ko) * 2018-11-05 2019-07-15 (주)씨엔티솔루션 복합소재기반의 표면 저항이 낮은 기능성 전선 및 그 제조방법

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CN101134841B (zh) * 2006-08-29 2010-09-01 广州金发科技股份有限公司 一种耐冲击的导电聚苯醚聚酰胺复合物及其制备方法
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KR102065559B1 (ko) 2020-01-13
CN107075262B (zh) 2020-05-12
CN107075262A (zh) 2017-08-18

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