WO2010134682A1 - Electrically conductive polyamide composite composition, and a fuel-conveying tube using the same - Google Patents

Electrically conductive polyamide composite composition, and a fuel-conveying tube using the same Download PDF

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WO2010134682A1
WO2010134682A1 PCT/KR2009/007981 KR2009007981W WO2010134682A1 WO 2010134682 A1 WO2010134682 A1 WO 2010134682A1 KR 2009007981 W KR2009007981 W KR 2009007981W WO 2010134682 A1 WO2010134682 A1 WO 2010134682A1
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polyamide
resin
copolymer
poly
ethylene
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French (fr)
Korean (ko)
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허진영
홍정숙
하두한
이영실
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제일모직 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present disclosure relates to conductive polyamide composite compositions and fuel transport tubes using the same.
  • the non-conductive polyamide resin composition mainly used in the conventional automotive fuel system is inferior in safety due to the friction between the tube and the fuel as the fuel circulates. Recently, a conductive material has been used for the tube to prevent such static electricity. In general, in order to impart conductivity to the polyamide resin, the conductive filler is added in a high content. In this case, the appearance is poor and expensive.
  • polyamide resin has been used for various applications in automotive interior and exterior parts because of excellent mechanical strength, wear resistance, heat resistance, chemical resistance, electrical insulation, arc resistance and the like.
  • a co-extrusion process such as a fuel tube or a hose
  • it is necessary to melt the rubber in the molding so that mixing of the rubber phase is required, and the compatibility, flexibility, viscosity, workability, etc. of the polyamide and rubber phase are required.
  • the application content of the carbon black for implementing the conductivity is usually 20% by weight or more, there was a technical limitation in the process to uniform dispersion of the rubber phase and the conductive filler of the tube.
  • One aspect of the present invention is to provide a conductive polyamide composite composition excellent in conductivity and compatibility.
  • Another aspect of the present invention is to provide a fuel transport tube made using the conductive polyamide composite composition.
  • One aspect of the invention is (A) 30 to 99% by weight of the first polymer comprising the polyamide resin (A-1) and (A-2) polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, olefin air 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of coalescing and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
  • the olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
  • the polyamide resin may be poly4-aminobutyl acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene do
  • the polyolefin resin is 0.94 kg / m 3 To 0.965 kg / m 3 High density polyethylene (HDPE) with a density of 0.91 kg / m 3 To 0.94 kg / m 3 Linear low density polyethylene (LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer, and combinations thereof.
  • HDPE High density polyethylene
  • LLDPE Linear low density polyethylene
  • the polyester resin may be prepared by mixing polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, and some other monomers in these resins. Qualitatively modified resins and combinations thereof.
  • the polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
  • EPDM ethylene-propylene diene copolymer resin
  • EPR ethylene-propylene rubber
  • the olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and the olefin-acrylate copolymer may be an ethylene methyl-acrylate copolymer or ethylene. Ethyl-acrylate copolymers, ethylene butyl-acrylate copolymers, ethylene vinyl-acrylate copolymers, and combinations thereof.
  • the olefin-maleic anhydride-modified copolymer may be selected from ethylene butene-maleic anhydride copolymer. Copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
  • the carbon black may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black, and combinations thereof.
  • the carbon nanotubes include single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes, and combinations thereof. It may be selected from the group consisting of.
  • Another aspect of the present invention provides a fuel transport tube made using the conductive polyamide composite composition.
  • Conductive polyamide composite composition according to an aspect of the present invention by using a mixture of carbon black and carbon nanotubes, the amount of the conductive filler is significantly reduced when manufacturing a fuel transport tube, the appearance is improved, economical, and excellent electrical conductivity Appears to prevent static electricity, and is excellent in various physical properties such as resistance to oil, tensile strength, impact strength and formability.
  • FIG. 1 is an electron micrograph showing a form in which carbon nanotubes are mixed with carbon black in a specimen using the conductive polyamide composite composition according to Example 4.
  • FIG. 1 is an electron micrograph showing a form in which carbon nanotubes are mixed with carbon black in a specimen using the conductive polyamide composite composition according to Example 4.
  • FIG. 2 is an electron micrograph showing a form in which carbon black is concentrated on a polyamide in a specimen using the conductive polyamide composite composition according to Comparative Example 3.
  • FIG. 2 is an electron micrograph showing a form in which carbon black is concentrated on a polyamide in a specimen using the conductive polyamide composite composition according to Comparative Example 3.
  • (A) 30 to 99% by weight of the first polymer comprising (A-1) polyamide resin and (A-2) polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of olefin copolymers and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
  • the base resin comprises a first polymer comprising (A-1) a polyamide resin, (A-2) a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer, It comprises a second polymer selected from the group consisting of a combination of these.
  • the first polymer according to an embodiment of the present invention comprises a polyamide resin, wherein the polyamide resin contains an amide group in the polymer main chain, and polymerizes with amino acids, lactams or diamines and dicarboxylic acids as main constituents.
  • Polyamide resin contains an amide group in the polymer main chain, and polymerizes with amino acids, lactams or diamines and dicarboxylic acids as main constituents.
  • amino acid examples include 6-aminocapronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.
  • lactam examples include ⁇ -caprolactam, ⁇ -laurolactam, and the like
  • diamine examples include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, and undecamethylene.
  • dicarboxylic acid examples include adipic acid, sericinic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic, or aromatic dicarboxylic acids, such as 5-sodium sulfoisophthalic acid, 2, 6- naphthalenedicarboxylic acid, hexahydro terephthalic acid, and hexahydroisophthalic acid, are mentioned.
  • Polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of mixtures, respectively.
  • polyamide resin examples include poly4-aminobutyric acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene
  • polyamide 4 examples include those selected from the group consisting of polyamide 4,6, polyamide 11 and combinations thereof, and more specifically, polyamide 11 may be used.
  • polyamide 11 it is highly resistant to gasoline and has low hygroscopicity.
  • the polyamide resin preferably has a melting point of 185 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol), and has a melting point and relative viscosity in the above range.
  • the mechanical properties and heat resistance of the polyamide composite composition are excellent.
  • polyamide resin may be used without limitation one or more types of polyamide having a glass transition temperature of 50 °C or more.
  • the first polymer including the polyamide resin may be included in an amount of 30 to 99 wt% based on the total amount of the base resin, and specifically, 55 to 99 wt%.
  • the first polymer containing the polyamide resin is included in the above range, it is excellent in conductivity, excellent physical properties such as tensile strength, impact strength, and can maintain the gasoline resistance at an appropriate level.
  • the base resin in addition to the first polymer including the polyamide resin, in the group consisting of polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, olefin-based copolymer, and combinations thereof to be described below
  • the second polymer selected is included together.
  • the second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof selectively disperses the conductive filler onto the polyamide resin in the conductive polyamide composite composition. Give the effect to be. This may serve to reduce the content of the conductive filler required to impart conductivity. Due to the use of the second polymer, by reducing the content of the conductive filler used in the conductive polyamide composite composition, it is possible to reduce the cost and economical, it is possible to implement a wide range of physical properties such as impact strength.
  • the hygroscopicity of the polyamide resin It improves the cost and reduces the cost of polyamide resin.
  • the conductive polyamide composite composition may be stabilized in the presence of the olefin copolymer according to a conventional production method.
  • the olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
  • the polyolefin resin is a high density polyethylene (HDPE) having a density of 0.94 kg / m 3 to 0.965 kg / m 3 , linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene, LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer and combinations thereof may be used.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene
  • polyester resin as the aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms can be used.
  • the alkyl means alkyl having 1 to 10 carbon atoms.
  • aromatic polyester resins include polyethylene terephthalate resins, polytrimethylene terephthalate resins, polybutylene terephthalate resins, polyhexamethylene terephthalate resins, polycyclohexane dimethylene terephthalate resins, and some others to these resins. It is possible to use a second polymer selected from the group consisting of a mixture of monomers and a resin modified to be amorphous, and more specifically, among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene tere Phthalate resin, amorphous polyethylene terephthalate resin, etc. can be used.
  • the polyester resin may have a range of intrinsic viscosity [ ⁇ ] of 0.85 kPa to 1.52 kPa / g, and specifically, may have a range of 1.03 kPa to 1.22 kPa / gk.
  • the polyester resin may have a specific gravity of 1.15 kPa to 1.4 g / cm 3, and may have a melting point of 210 kPa to 280 ° C.
  • the polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
  • EPDM ethylene-propylene diene copolymer resin
  • EPR ethylene-propylene rubber
  • the olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and specifically, an olefin-maleic anhydride modified copolymer may be used.
  • an olefin-maleic anhydride modified copolymer may be used.
  • compatibility with the second polymer selected from the group consisting of polyamide resin, polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, and combinations thereof can be effectively imparted. .
  • the olefin-acrylate copolymer is selected from the group consisting of ethylene methyl-acrylate copolymer, ethylene ethyl-acrylate copolymer, ethylene butyl-acrylate copolymer, ethylene vinyl-acrylate copolymer and combinations thereof. Can be used.
  • the olefin-maleic anhydride modified copolymer may be selected from the group consisting of ethylene butene-maleic anhydride copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
  • the olefin-maleic anhydride-modified copolymer may include 0.1 to 10 parts by weight of maleic anhydride with respect to 100 parts by weight of a main chain, specifically, 0.5 to 5 parts by weight.
  • maleic anhydride branch is contained in the said range, it is advantageous for physical properties, such as the compatibility improvement of polyamide resin and polyolefin resin which are basic resins.
  • the second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof may be included in an amount of 1 to 70 wt% based on 100 parts by weight of the base resin. It may be included in 15 to 60% by weight.
  • the second polymer is included in the above range, not only excellent mechanical strength and impact strength can be secured, but also excellent conductivity and resistance to gasoline.
  • the compatibility of the polyamide resin with a second polymer selected from the group consisting of polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin and combinations thereof It is excellent in this, and does not form its own phase which consists only of an olefin type copolymer, and can obtain uniform dispersion as a whole, and its external appearance is good.
  • Carbon black according to an embodiment of the present invention may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black and combinations thereof Among them, specifically, ketjen black may be used, which is more conductive.
  • the carbon black particles 10 to 30 nm in diameter are agglomerated with each other in a size of 10 ⁇ m to implement conductivity.
  • the carbon black may be included in an amount of 1 to 15 parts by weight, and specifically 5 to 10 parts by weight based on 100 parts by weight of the base resin.
  • the conductivity is excellent, thereby lowering the content of the filler for the conductivity can be economical, it is easy to implement excellent physical properties.
  • Carbon nanotubes according to an embodiment of the present invention is a single wall carbon nanotube (single wall carbon nanotube), double wall carbon nanotube (double wall carbon nanotube), multi-wall carbon nanotube (multi wall carbon nanotube) tube) and combinations thereof.
  • the carbon nanotubes may be included in an amount of 0.01 to 5 parts by weight, specifically 0.1 to 1 part by weight, based on 100 parts by weight of the base resin.
  • the physical properties of the base resin for example, mechanical strength such as tensile strength, thermal stability, and the like can be maintained.
  • the conductive polyamide composite composition according to the embodiment of the present invention significantly reduced the amount of the conductive filler by using a mixture of carbon black and carbon nanotubes. This improved the dispersion efficiency of additives such as compatibilizers.
  • Carbon nanotubes have a disadvantage in that they are difficult to disperse during the process due to their large aspect ratio (aspect ratio> 100). Therefore, a high dispersion melt mixer should be used in the melt mixing step to increase dispersion efficiency.
  • the conductive polyamide composite composition according to the embodiment of the present invention may include a resin stabilizer, a plasticizer, or the like as an additive.
  • the resin stabilizer may include, for example, a first polymer comprising a polyamide resin included in the conductive polyamide composite composition, a polyolefin resin, and a polyester in the process of manufacturing a molded article from the conductive polyamide composite composition by extrusion or injection. It stabilizes a second polymer selected from the group consisting of resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers, and combinations thereof to serve to inhibit decomposition (eg, pyrolysis) or reaction of these resins with each other.
  • a first polymer comprising a polyamide resin included in the conductive polyamide composite composition, a polyolefin resin, and a polyester in the process of manufacturing a molded article from the conductive polyamide composite composition by extrusion or injection.
  • a second polymer selected from the group consisting of resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers,
  • a second polymer selected from the group consisting of polyamide resins, polyolefin resins, polyester resins, polyolefin-based thermoplastic elastomer resins, olefin copolymers, and combinations thereof in the conductive polyamide composite composition may be Its properties can be better expressed, and the thermal stability, moldability, etc. of the conductive polyamide composite composition can be further improved.
  • the resin stabilizer any conventionally known resin stabilizer can be used without limitation.
  • the resin stabilizer may be phosphoric acid, triphenylphosphite, trimethylphosphite, triisodecylphosphite, tri- (2,4-di-t-butylphenyl) phosphite, 3,5-di-t -Butyl-4-hydroxybenzylphosphonic acid, tetrakis propionate methane, and combinations thereof.
  • the plasticizer not only improves the flowability and moldability of the conductive polyamide composite composition, but also improves the dispersion of carbon nanotubes and carbon black.
  • the plasticizer may be ethylene bis-stearamide, pentaerythritol, polycarprolactone, high density polyethylene (HDPE), caster oil, o-toluene Ortho-toluene sulfonamide, p-toluene sulfonamide And combinations thereof may be selected from the group consisting of.
  • the molded article may be manufactured through a conventional method of mixing the above-described components to prepare a conductive polyamide composite composition and melt extruding the prepared conductive polyamide composite composition in a mixer.
  • the conductive polyamide composite composition is 60 At ⁇ ⁇ , the surface resistance was maintained at 10 7 dl / cm 2 under immersion of 20% ethanol and fuel, showing an excellent antistatic effect.
  • the conductive polyamide composite composition is excellent in various physical properties such as moldability, chemical resistance, impact properties. That is, the conductive polyamide composite composition is excellent in overall physical properties such as not only conductivity but also moldability, so that the conductive polyamide composite can be used in high volatility fuel transport tubes and can be applied to various fields of automotive fuel systems. Can be provided.
  • a fuel transport tube made using the conductive polyamide composite composition described above.
  • the fuel transport tube comprises a first polymer comprising a polyamide resin and a base resin comprising a second polymer selected from the group consisting of polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins, olefin copolymers, and combinations thereof. And an olefin copolymer, carbon black, carbon nanotube, and optionally a resin stabilizer and a plasticizer dispersed in the base resin.
  • the fuel transport tube by using a conductive polyamide composite composition according to an embodiment of the present invention by producing a molded article comprising carbon black and carbon nanotubes, the carbon of several microns size is uniformly dispersed in the molded article By effectively connecting the carbon nanotubes between the black can realize electrical conductivity.
  • these plastic molded articles have excellent physical properties such as moldability, thermal stability and chemical resistance.
  • A-2-1 polyolefin resin which is a 1st polymer containing (A-1) polyamide resin and (A-2) 2nd polymer as (A) base resin used by the Example and comparative example which are mentioned later,
  • A-2-2 polyester resin,
  • A-2-4 olefin copolymer
  • B carbon black
  • C carbon nanotube
  • Polyamide 11 (BESNO P40TL, manufactured by Arkema) having a viscosity measured at 220 ° C. of 10,000 [Pa ⁇ s] (0.1 [1 / s] condition) or more was used.
  • Linear low-density polyethylene (4222F from Samsung Total) having a weight average molecular weight (Mw) of 1,000 ⁇ g / mol or more was used.
  • Shinite K001 manufactured by SHINONG CORPORATION having a specific gravity of 1.31 g / cm 3, a melting point of 228 ° C., and an intrinsic viscosity of 0.83 was used.
  • Ethylene-propylene diene copolymer resin (EPDM KEP020P from Kumho Petrochemical) was used.
  • Ethylene butene-maleic anhydride copolymer (Fusabond MN493D from DuPont) was used.
  • Multi-walled carbon nanotubes with tube diameters from 1 mm to 30 nm are used.
  • Nanocyl NC7000 was used as the multi-walled carbon nanotube.
  • the conductive polyamide composite compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 were melt kneaded in a twin screw melt extruder heated to 250 ° C. to prepare pellets.
  • the pellet was dried at 100 ° C. for 4 hours, and then ASTM specimens for mechanical properties and conductivity evaluation, such as flexural strength, tensile strength and impact strength, were prepared using a screw-type injection machine heated to 250 ° C.
  • the dispersion of carbon black and carbon nanotubes was observed in the specimen of Example 4 using a transmission electron microscope (TEM), and the results are shown in FIG. 1.
  • TEM transmission electron microscope
  • the dispersibility of carbon black was observed in the specimen of Comparative Example 2 and shown in FIG. 2.
  • the carbon black in the first polymer comprising a polyamide resin and the second polymer selected from the group consisting of a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer and a combination thereof
  • melt mixing the carbon nanotubes in an amount in the range according to an embodiment of the present invention it was confirmed that the conductivity and mechanical properties are excellent.
  • the compatibility of the conductive polyamide composite is increased, and thus the impact reinforcing effect was exhibited.
  • Carbon nanotubes can act as an electrical bridge (electrical bridge) between the carbon black particles to reduce the content of the conductive filler contained for the conductive implementation.
  • Dispersion of carbon black is shown by expanding the comparative example 2 to a high magnification (see FIG. 2), and most of the carbon black is located in the polyamide resin, particularly concentrated at the interface between the resins, and polyolefin resin, polyester resin, polyolefin-based It is hardly observed on the thermoplastic elastomer resin or the olefin copolymer.
  • the conductivity of the molded article to which the conductive polyamide composite composition according to one embodiment of the present invention is applied is a mixture of carbon black and carbon nanotubes, whereby carbon black and carbon nanotubes are polyolefin resins, polyester resins, and polyolefins. It has a higher affinity for a polyamide resin than a thermoplastic elastomer resin or an olefin copolymer and is concentrated in the periphery of the polyamide resin.
  • the carbon nanotubes electrically connect the carbon black particles, so that the content of a low conductive filler The conductivity could be secured.
  • the specimens of Examples 1 to 4 exhibit tensile strength through effective dispersion of carbon black and carbon nanotubes and commercialization of polyamide resins, polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins or olefin copolymers. Mechanical properties such as impact strength and impact were excellent overall.

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Abstract

The present invention relates to an electrically conductive polyamide composite composition comprising: (A) a base resin comprising (A-1) a first polymer comprising a polyamide resin and (A-2) a second polymer selected from the group consisting of polyolefin resins, polyester resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers and combinations thereof; (B) carbon black; and (C) carbon nanotubes. The present invention also relates to a fuel-conveying tube using the electrically conductive polyamide composite composition.

Description

전도성 폴리아미드 복합체 조성물 및 이를 이용한 연료 수송 튜브Conductive Polyamide Composite Composition and Fuel Transport Tube Using the Same
본 기재는 전도성 폴리아미드 복합체 조성물 및 이를 이용한 연료 수송 튜브에 관한 것이다. 　The present disclosure relates to conductive polyamide composite compositions and fuel transport tubes using the same.
종래의 자동차 연료 시스템에서 주로 사용되는 비전도성 폴리아미드 수지 조성물은 연료가 순환하면서 튜브와 연료 사이의 마찰에 의하여 정전기가 발생할 수 있어 안전성이 떨어진다. 　최근에는 이러한 정전기 방지를 위하여 전도성을 띤 소재가 튜브에 이용되고 있다. 　일반적으로 폴리아미드 수지에 전도성을 부여하기 위하여 전도성 필러를 높은 함량으로 첨가하게 되는데, 이 경우 외관이 불량하고 고가인 단점이 있다. 　The non-conductive polyamide resin composition mainly used in the conventional automotive fuel system is inferior in safety due to the friction between the tube and the fuel as the fuel circulates. Recently, a conductive material has been used for the tube to prevent such static electricity. In general, in order to impart conductivity to the polyamide resin, the conductive filler is added in a high content. In this case, the appearance is poor and expensive.
일반적으로 폴리아미드 수지는 기계적 강도, 내마모성, 내열성, 내약품성, 전기 절연성, 내아크성 등이 우수하여 자동차 내·외장재용 부품에 여러 용도로 사용되어 왔다. 　연료 튜브나 호스와 같이 공압출(co-extrusion) 프로세스를 통해 성형되는 경우, 성형상 용융 탄성을 요구하여 고무상의 혼합이 필요하고, 폴리아미드와 고무상의 상용성, 유연성, 점도, 작업성 등이 문제가 되어 적용이 제한적이었다. 　특히, 전도성을 구현하기 위한 카본블랙의 적용 함량이 통상적으로 20 중량% 이상으로서, 튜브의 고무상과 전도성 필러의 분산을 균일하게 하는데 공정상 기술적 한계가 있었다. In general, polyamide resin has been used for various applications in automotive interior and exterior parts because of excellent mechanical strength, wear resistance, heat resistance, chemical resistance, electrical insulation, arc resistance and the like. In the case of molding through a co-extrusion process such as a fuel tube or a hose, it is necessary to melt the rubber in the molding, so that mixing of the rubber phase is required, and the compatibility, flexibility, viscosity, workability, etc. of the polyamide and rubber phase are required. It was a problem and the application was limited. In particular, the application content of the carbon black for implementing the conductivity is usually 20% by weight or more, there was a technical limitation in the process to uniform dispersion of the rubber phase and the conductive filler of the tube.
본 발명의 일 측면은 전도성 및 상용성이 우수한 전도성 폴리아미드 복합체 조성물을 제공하기 위한 것이다. 　One aspect of the present invention is to provide a conductive polyamide composite composition excellent in conductivity and compatibility.
본 발명의 다른 측면은 상기 전도성 폴리아미드 복합체 조성물을 이용하여 제조된 연료 수송 튜브를 제공하기 위한 것이다. 　Another aspect of the present invention is to provide a fuel transport tube made using the conductive polyamide composite composition.
본 발명의 일 측면은 (A) (A-1) 폴리아미드 수지를 포함하는 제 1 폴리머 30 내지 99 중량% 및 (A-2) 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머 1 내지 70 중량%를 포함하는 기초 수지 100 중량부; (B) 카본블랙 1 내지 15 중량부; 및 (C) 탄소나노튜브 0.01 내지 5 중량부를 포함하는 전도성 폴리아미드 복합체 조성물을 제공한다. One aspect of the invention is (A) 30 to 99% by weight of the first polymer comprising the polyamide resin (A-1) and (A-2) polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, olefin air 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of coalescing and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
상기 올레핀계 공중합체는 상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 수지 100 중량부에 대하여 65 내지 100 중량부로 포함될 수 있다. The olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
상기 폴리아미드 수지는 폴리4-아미노부틸산(poly(4-aminobutyric acid), 폴리아미드 4); 폴리카프로락탐(polycaprolactam, 폴리아미드 6); 폴리7-아미노헵탄산(poly(7-aminoheptanoic acid), 폴리아미드 7); 폴리8-아미노옥탄산(poly(8-aminoocatanoic acid); 폴리아미드 8); 폴리9-아미노노난산(poly(9-aminononanoic acid), 폴리아미드 9); 폴리10-아미노데칸산(poly(10-aminodecanoic acid), 폴리아미드 10); 폴리(11-아미노운데칸산)(poly(11-aminoundecanoic acid), 폴리아미드 11); 폴리라우릴락탐(polylaurylactam, 폴리아미드 12); 폴리테트라메틸렌 아디프아미드(poly(tetramethylene adipamide), 폴리아미드 4,6); 폴리헥사메틸렌 아디프아미드(poly(hexamethylene adipamide), 폴리아미드 6,6); 폴리헥사메틸렌 아젤아미드(poly(hexamethylene azelamide), 폴리아미드 6,9); 폴리헥사메틸렌 세바카미드(poly(hexamethylene sebacamide), 폴리아미드 6,10); 폴리헥사메틸렌 도데카노디아미드(poly(hexamethylene dodecanodiamide), 폴리아미드 6,12); 폴리헵타메틸렌 피멜아미드(poly(heptamethylene pimelamide), 폴리아미드 7,7); 폴리옥타메틸렌 수베라미드(poly(octamethylene suberamide), 폴리아미드 8,8); 폴리노나메틸렌 아젤아미드(poly(nonamethylene azelamide), 폴리아미드 9,9); 폴리데카메틸렌 아젤아미드(poly(decamethylene azelamide), 폴리아미드 10,9); 폴리아미드 6/6,10 공중합체; 폴리아미드 6/6,6 공중합체; 폴리아미드 6/12 공중합체; 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　The polyamide resin may be poly4-aminobutyl acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene dodecanodiamide (poly (hexamethylene dodecanodiamide), polyamide 6,12); Polyheptaethylene pimelamide (polyamide 7,7); Polyoctamethylene subberamide (poly (octamethylene suberamide), polyamide 8,8); Poly (nonamethylene azelamide), polyamide 9,9; Polydecamethylene azelamide (polyamide 10,9); Polyamide 6 / 6,10 copolymer; Polyamide 6 / 6,6 copolymer; Polyamide 6/12 copolymer; And combinations thereof may be selected from the group consisting of.
상기 폴리올레핀 수지는 0.94 kg/m3 내지 0.965 kg/m3 의 밀도를 갖는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 0.91 kg/m3 내지 0.94 kg/m3의 밀도를 갖는 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 폴리프로필렌, 에틸렌-비닐알코올 공중합체, 에틸렌-프로필렌 공중합체 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The polyolefin resin is 0.94 kg / m3 To 0.965 kg / m3                      High density polyethylene (HDPE) with a density of 0.91 kg / m3 To 0.94 kg / m3Linear low density polyethylene (LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer, and combinations thereof.
상기 폴리에스테르 수지는 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리헥사메틸렌 테레프탈레이트 수지, 폴리시클로헥산 디메틸렌 테레프탈레이트 수지, 이들 수지에 일부 다른 단량체를 혼합하여 비결정성으로 개질한 수지 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The polyester resin may be prepared by mixing polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, and some other monomers in these resins. Qualitatively modified resins and combinations thereof.
상기 폴리올레핀계 열가소성 탄성체 수지는 에틸렌-프로필렌 디엔 공중합체 수지(EPDM), 에틸렌-프로필렌 고무(EPR) 및 이들의　조합으로 이루어진 군에서 선택될 수 있다. 　The polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
상기 올레핀계 공중합체는 올레핀-아크릴레이트 공중합체, 올레핀-무수말레인산 변성 공중합체 및 이들의 조합으로 이루어진 군에서 선택될 수 있으며, 상기 올레핀-아크릴레이트 공중합체는 에틸렌 메틸-아크릴레이트 공중합체, 에틸렌 에틸-아크릴레이트 공중합체, 에틸렌 부틸-아크릴레이트 공중합체, 에틸렌 비닐-아크릴레이트 공중합체 및 이들의 조합으로 이루어진 군에서 선택될 수 있으며, 상기 올레핀-무수말레인산 변성 공중합체는 에틸렌 부텐-무수말레인산 공중합체, 에틸렌 옥텐-무수말레인산 공중합체, 에틸렌 프로필렌-무수말레인산 공중합체 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and the olefin-acrylate copolymer may be an ethylene methyl-acrylate copolymer or ethylene. Ethyl-acrylate copolymers, ethylene butyl-acrylate copolymers, ethylene vinyl-acrylate copolymers, and combinations thereof. The olefin-maleic anhydride-modified copolymer may be selected from ethylene butene-maleic anhydride copolymer. Copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
상기 카본블랙은 케첸 블랙(ketjen black), 아세틸렌 블랙(acetylene black), 퍼니스 블랙(furnace black), 채널 블랙(channel black) 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The carbon black may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black, and combinations thereof.
상기 탄소나노튜브는 단일벽 탄소나노튜브(single wall carbon nano-tube), 이중벽 탄소나노튜브(double wall carbon nano-tube), 다중벽 탄소나노튜브 (multi wall carbon nano-tube) 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The carbon nanotubes include single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes, and combinations thereof. It may be selected from the group consisting of.
　
본 발명의 다른 측면은 상기 전도성 폴리아미드 복합체 조성물을 이용하여 제조된　연료 수송 튜브를 제공한다.Another aspect of the present invention provides a fuel transport tube made using the conductive polyamide composite composition.
기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Other details of aspects of the invention are included in the following detailed description.
본 발명의 일 측면에 따른 전도성 폴리아미드 복합체 조성물은 카본블랙과 탄소나노튜브를 혼합하여 사용함으로써, 연료 수송 튜브로 제조 시 전도성 필러의 사용량이 획기적으로 줄어 외관이 개선되고 경제적이며, 우수한 전기 전도성을 발현하여 정전기를 방지하고, 내가솔린성, 인장강도, 충격강도, 성형성 등의 제반 물성이 우수하다. Conductive polyamide composite composition according to an aspect of the present invention by using a mixture of carbon black and carbon nanotubes, the amount of the conductive filler is significantly reduced when manufacturing a fuel transport tube, the appearance is improved, economical, and excellent electrical conductivity Appears to prevent static electricity, and is excellent in various physical properties such as resistance to oil, tensile strength, impact strength and formability.
도 1은 실시예 4에 따른 전도성 폴리아미드 복합체 조성물을 이용한 시편에서, 탄소나노튜브가 카본블랙과 혼입된 형태를 보여주는 전자 현미경 사진이다. 　1 is an electron micrograph showing a form in which carbon nanotubes are mixed with carbon black in a specimen using the conductive polyamide composite composition according to Example 4. FIG.
도 2는 비교예 3에 따른 전도성 폴리아미드 복합체 조성물을 이용한 시편에서, 카본블랙이 폴리아미드 상에 집중적으로 분포되어 있는 형태를 보여주는 전자 현미경 사진이다. 　　FIG. 2 is an electron micrograph showing a form in which carbon black is concentrated on a polyamide in a specimen using the conductive polyamide composite composition according to Comparative Example 3. FIG.
이하에서 본 발명의 구현예를 보다 상세하게 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다. 　Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 발명의 일 구현예에 따르면, (A) (A-1) 폴리아미드 수지를 포함하는 제 1 폴리머 30 내지 99 중량% 및 (A-2) 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머 1 내지 70 중량%를 포함하는 기초 수지 100 중량부; (B) 카본블랙 1 내지 15 중량부; 및 (C) 탄소나노튜브 0.01 내지 5 중량부를 포함하는 전도성 폴리아미드 복합체 조성물을 제공한다. 　 　According to one embodiment of the invention, (A) 30 to 99% by weight of the first polymer comprising (A-1) polyamide resin and (A-2) polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of olefin copolymers and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
이하, 본 발명의 일 구현예에 따른 전도성 폴리아미드 복합체 조성물을 이루는 각 성분에 대하여 구체적으로 살펴본다. Hereinafter, each component of the conductive polyamide composite composition according to one embodiment of the present invention will be described in detail.
(A) 기초 수지(A) basic resin
본 발명의 일 구현예에 따른 기초 수지는 (A-1) 폴리아미드 수지를 포함하는 제 1 폴리머와, (A-2) 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머를 포함하여 이루어진다. 　The base resin according to an embodiment of the present invention comprises a first polymer comprising (A-1) a polyamide resin, (A-2) a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer, It comprises a second polymer selected from the group consisting of a combination of these.
(A-1) 제 1 폴리머(A-1) first polymer
본 발명의 일 구현예에 따른 제 1 폴리머는 폴리아미드 수지를 포함하고, 상기 폴리아미드 수지는 고분자 주쇄에 아미드기를 함유한 것으로서, 아미노산, 락탐 또는 디아민과 디카르복실산을 주된 구성 성분으로 하여 중합된 폴리아미드 수지이다.The first polymer according to an embodiment of the present invention comprises a polyamide resin, wherein the polyamide resin contains an amide group in the polymer main chain, and polymerizes with amino acids, lactams or diamines and dicarboxylic acids as main constituents. Polyamide resin.
상기 아미노산의 구체적인 예로는 6-아미노카프론산, 11-아미노운데칸산, 12-아미노도데칸산, 파라아미노메틸벤조산 등을 들 수 있다. 　상기 락탐의 구체적인 예로는 ε-카프로락탐, ω-라우로락탐 등을 들 수 있으며, 상기 디아민의 구체적인 예로는 테트라메틸렌디아민, 헥사메틸렌디아민, 2-메틸펜타메틸렌디아민, 노나메틸렌디아민, 운데카메틸렌디아민, 도데카메틸렌디아민, 2,2,4-트리메틸헥사메틸렌디아민, 2,4,4-트리메틸헥사메틸렌디아민, 5-메틸노나메틸렌디아민, 메타크실렌디아민, 파라크실렌디아민, 1,3-비스(아미노메틸)시클로헥산, 1,4-비스(아미노메틸)시클로헥산, 1-아미노-3-아미노메틸-3,5,5-트리메틸시클로헥산, 비스(4-아미노시클로헥실)메탄, 비스(3-메틸-4-아미노시클로헥실)메탄, 2,2-비스(4-아미노시클로헥실)프로판, 비스(아미노프로필)피페라진, 아미노에틸피페라진 등의 지방족, 지환족 또는 방향족의 디아민을 들 수 있다. 　또한 상기 디카르복실산의 구체적인 예로는 아디프산, 스베린산, 아젤라산, 세바스산, 도데칸2산, 테레프탈산, 이소프탈산, 2-클로로테레프탈산, 2-메틸테레프탈산, 5-메틸이소프탈산, 5-나트륨설포이소프탈산, 2,6-나프탈렌디카르복실산, 헥사히드로테레프탈산, 헥사히드로이소프탈산 등의 지방족, 지환족 또는 방향족의 디카르복실산을 들 수 있다. 　이들의 원료로부터 유도되는 폴리아미드 호모폴리머 또는 코폴리머를 각각 단독 또는 혼합물의 형태로 이용할 수 있다.Specific examples of the amino acid include 6-aminocapronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Specific examples of the lactam include ε-caprolactam, ω-laurolactam, and the like, and specific examples of the diamine include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, and undecamethylene. Diamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, methaxylenediamine, paraxylenediamine, 1,3-bis ( Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3 Aliphatic, alicyclic or aromatic diamines such as -methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine have. Specific examples of the dicarboxylic acid include adipic acid, sericinic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic, or aromatic dicarboxylic acids, such as 5-sodium sulfoisophthalic acid, 2, 6- naphthalenedicarboxylic acid, hexahydro terephthalic acid, and hexahydroisophthalic acid, are mentioned. Polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of mixtures, respectively.
상기 폴리아미드 수지의 구체적인 예로는, 폴리4-아미노부틸산(poly(4-aminobutyric acid), 폴리아미드 4); 폴리카프로락탐(polycaprolactam, 폴리아미드 6); 폴리7-아미노헵탄산(poly(7-aminoheptanoic acid), 폴리아미드 7); 폴리8-아미노옥탄산(poly(8-aminoocatanoic acid); 폴리아미드 8); 폴리9-아미노노난산(poly(9-aminononanoic acid), 폴리아미드 9); 폴리10-아미노데칸산(poly(10-aminodecanoic acid), 폴리아미드 10); 폴리(11-아미노운데칸산)(poly(11-aminoundecanoic acid), 폴리아미드 11); 폴리라우릴락탐(polylaurylactam, 폴리아미드 12); 폴리테트라메틸렌 아디프아미드(poly(tetramethylene adipamide), 폴리아미드 4,6); 폴리헥사메틸렌 아디프아미드(poly(hexamethylene adipamide), 폴리아미드 6,6); 폴리헥사메틸렌 아젤아미드(poly(hexamethylene azelamide), 폴리아미드 6,9); 폴리헥사메틸렌 세바카미드(poly(hexamethylene sebacamide), 폴리아미드 6,10); 폴리헥사메틸렌 도데카노디아미드(poly(hexamethylene dodecanodiamide), 폴리아미드 6,12); 폴리헵타메틸렌 피멜아미드(poly(heptamethylene pimelamide), 폴리아미드 7,7); 폴리옥타메틸렌 수베라미드(poly(octamethylene suberamide), 폴리아미드 8,8); 폴리노나메틸렌 아젤아미드(poly(nonamethylene azelamide), 폴리아미드 9,9); 폴리데카메틸렌 아젤아미드(poly(decamethylene azelamide), 폴리아미드 10,9); 폴리아미드 6/6,10 공중합체; 폴리아미드 6/6,6 공중합체; 폴리아미드 6/12 공중합체; 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　이 중, 구체적으로는 폴리아미드 4,6, 폴리아미드 11 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있으며, 더 구체적으로는 폴리아미드 11을 사용할 수 있다. 　폴리아미드 11을 사용하는 경우 내가솔린성이 높고 흡습성이 낮다. Specific examples of the polyamide resin include poly4-aminobutyric acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene dodecanodiamide (poly (hexamethylene dodecanodiamide), polyamide 6,12); Polyheptaethylene pimelamide (polyamide 7,7); Polyoctamethylene subberamide (poly (octamethylene suberamide), polyamide 8,8); Poly (nonamethylene azelamide), polyamide 9,9; Polydecamethylene azelamide (polyamide 10,9); Polyamide 6 / 6,10 copolymer; Polyamide 6 / 6,6 copolymer; Polyamide 6/12 copolymer; And combinations thereof may be selected from the group consisting of. Among them, specifically, those selected from the group consisting of polyamide 4,6, polyamide 11 and combinations thereof may be used, and more specifically, polyamide 11 may be used. In the case of using polyamide 11, it is highly resistant to gasoline and has low hygroscopicity.
상기 폴리아미드 수지는 융점이 185 ℃ 이상이고, 상대점도(m-크레졸에 폴리아미드 수지 1 중량%를 첨가하여 25 ℃에서 측정)가 2 이상인 것이 좋으며, 상기 범위의 융점 및 상대점도를 가지는 경우 전도성 폴리아미드 복합체 조성물의 기계적 특성과 내열성이 우수하다.The polyamide resin preferably has a melting point of 185 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol), and has a melting point and relative viscosity in the above range. The mechanical properties and heat resistance of the polyamide composite composition are excellent.
또한 상기 폴리아미드 수지는 유리전이온도가 50 ℃ 이상인 한 종류 이상의 폴리아미드를 제한 없이 사용할 수 있다. 　In addition, the polyamide resin may be used without limitation one or more types of polyamide having a glass transition temperature of 50 ℃ or more.
상기 폴리아미드 수지를 포함하는 제 1 폴리머는 기초 수지 총량에 대하여 30 내지 99 중량%로 포함될 수 있으며, 구체적으로는 55 내지 99 중량%로 포함될 수 있다. 　폴리아미드 수지를 포함하는 제 1 폴리머가 상기 범위 내로 포함되는 경우, 전도성이 우수하고, 인장강도, 충격강도 등의 제반 물성이 우수하며, 내가솔린성을 적정 수준으로 유지할 수 있다.The first polymer including the polyamide resin may be included in an amount of 30 to 99 wt% based on the total amount of the base resin, and specifically, 55 to 99 wt%. When the first polymer containing the polyamide resin is included in the above range, it is excellent in conductivity, excellent physical properties such as tensile strength, impact strength, and can maintain the gasoline resistance at an appropriate level.
　
(A-2) 제 2 폴리머(A-2) second polymer
본 발명의 일 구현예에 따른 기초 수지에는 상기 폴리아미드 수지를 포함하는 제 1 폴리머 이외에 하기 설명할 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머가 함께 포함된다. 　In the base resin according to an embodiment of the present invention, in addition to the first polymer including the polyamide resin, in the group consisting of polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, olefin-based copolymer, and combinations thereof to be described below The second polymer selected is included together.
상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머 는 전도성 폴리아미드 복합체 조성물 내에서 전도성 필러를 폴리아미드 수지 상으로 선택적으로 분산되도록 하는 효과를 부여한다. 　이로써 전도성을 부여하는데 요구되는 전도성 필러의 함량을 감량시키는 역할을 할 수 있다. 　상기 제 2 폴리머의 사용으로 인하여, 상기 전도성 폴리아미드 복합체 조성물에 사용되는 전도성 필러의 함량이 감량됨으로써 원가를 절감하여 경제적이고, 충격강도 등 제반 물성을 폭 넓게 구현할 수 있다. 　The second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof selectively disperses the conductive filler onto the polyamide resin in the conductive polyamide composite composition. Give the effect to be. This may serve to reduce the content of the conductive filler required to impart conductivity. Due to the use of the second polymer, by reducing the content of the conductive filler used in the conductive polyamide composite composition, it is possible to reduce the cost and economical, it is possible to implement a wide range of physical properties such as impact strength.
또한 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머 를 폴리아미드 수지를 포함하는 제 1 폴리머와 혼합함으로써, 폴리아미드 수지의 흡습성을 개선하고, 폴리아미드 수지의 함량을 줄여 원가를 감소하는 효과를 가져온다. 　In addition, by adsorbing a second polymer selected from the group consisting of polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins, olefin copolymers, and combinations thereof with the first polymer containing a polyamide resin, the hygroscopicity of the polyamide resin It improves the cost and reduces the cost of polyamide resin.
상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지는 폴리아미드 수지와 상용성이 떨어지므로, 통상적인 제조 방법에 따라 올레핀계 공중합체의 존재 하에 전도성 폴리아미드 복합체 조성물을 안정화시킬 수 있다. 　Since the polyolefin resin, the polyester resin, and the polyolefin thermoplastic elastomer resin are incompatible with the polyamide resin, the conductive polyamide composite composition may be stabilized in the presence of the olefin copolymer according to a conventional production method.
여기서, 상기 올레핀계 공중합체는, 상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 수지 100 중량부에 대하여 65 내지 100 중량부로 포함될 수 있다. Herein, the olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
상기 폴리올레핀 수지는 0.94 kg/m3 내지 0.965 kg/m3의 밀도를 갖는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 0.91 kg/m3 내지 0.94 kg/m3의 밀도를 갖는 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 폴리프로필렌, 에틸렌-비닐알코올 공중합체, 에틸렌-프로필렌 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. The polyolefin resin is a high density polyethylene (HDPE) having a density of 0.94 kg / m 3 to 0.965 kg / m 3 , linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene, LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer and combinations thereof may be used.
상기 폴리에스테르 수지는 방향족 폴리에스테르 수지로서, 테레프탈산 또는 테레프탈산 알킬 에스테르와 2 내지 10개의 탄소 원자를 갖는 글리콜 성분으로부터 용융 중합에 의하여 축중합된 수지를 사용할 수 있다. 　이때 상기 알킬은 탄소수 1 내지 10의 알킬을 의미한다. 　As the polyester resin, as the aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms can be used. In this case, the alkyl means alkyl having 1 to 10 carbon atoms.
이러한 방향족 폴리에스테르 수지의 구체적인 예로는, 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리헥사메틸렌 테레프탈레이트 수지, 폴리시클로헥산 디메틸렌 테레프탈레이트 수지, 이들 수지에 일부 다른 단량체를 혼합하여 비결정성으로 개질한 수지 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머를 사용할 수 있으며, 이들 중에서 더 구체적으로는 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 비결정성 폴리에틸렌 테레프탈레이트 수지 등을 사용할 수 있다.Specific examples of such aromatic polyester resins include polyethylene terephthalate resins, polytrimethylene terephthalate resins, polybutylene terephthalate resins, polyhexamethylene terephthalate resins, polycyclohexane dimethylene terephthalate resins, and some others to these resins. It is possible to use a second polymer selected from the group consisting of a mixture of monomers and a resin modified to be amorphous, and more specifically, among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene tere Phthalate resin, amorphous polyethylene terephthalate resin, etc. can be used.
상기 폴리에스테르 수지는 고유점도[η]가 0.85　내지 1.52 ㎗/g 의 범위를 가질 수 있으며, 구체적으로는 1.03　내지 1.22 ㎗/g　의 범위를 가질 수 있다. 　또한 상기 폴리에스테르 수지는 비중이 1.15　내지 1.4 g/㎤ 의 범위를 가질 수 있으며, 융점이 210　내지 280 ℃ 의 범위를 가질 수 있다. 　폴리에스테르 수지가 상기 범위의 고유점도, 비중 및 융점을 가지는 경우 우수한 기계적 물성과 성형성을 확보할 수 있다.The polyester resin may have a range of intrinsic viscosity [η] of 0.85 kPa to 1.52 kPa / g, and specifically, may have a range of 1.03 kPa to 1.22 kPa / gk. In addition, the polyester resin may have a specific gravity of 1.15 kPa to 1.4 g / cm 3, and may have a melting point of 210 kPa to 280 ° C. When the polyester resin has intrinsic viscosity, specific gravity, and melting point in the above range, it is possible to secure excellent mechanical properties and moldability.
상기 폴리올레핀계 열가소성 탄성체 수지는 에틸렌-프로필렌 디엔 공중합체 수지(EPDM), 에틸렌-프로필렌 고무(EPR) 및 이들의　조합으로 이루어진 군에서 선택될 수 있다. 　The polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
상기 올레핀계 공중합체는 올레핀-아크릴레이트 공중합체, 올레핀-무수말레인산 변성 공중합체 및 이들의 조합으로 이루어진 군에서 선택하여 사용할 수 있으며, 이 중 구체적으로는 올레핀-무수말레인산 변성 공중합체를 사용할 수 있다. 　올레핀-무수말레인산 변성 공중합체를 사용하는 경우 폴리아미드 수지와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머와의 상용성을 효과적으로 부여할 수 있다. 　The olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and specifically, an olefin-maleic anhydride modified copolymer may be used. . When the olefin-maleic anhydride modified copolymer is used, compatibility with the second polymer selected from the group consisting of polyamide resin, polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, and combinations thereof can be effectively imparted. .
상기 올레핀-아크릴레이트 공중합체는 에틸렌 메틸-아크릴레이트 공중합체, 에틸렌 에틸-아크릴레이트 공중합체, 에틸렌 부틸-아크릴레이트 공중합체, 에틸렌 비닐-아크릴레이트 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The olefin-acrylate copolymer is selected from the group consisting of ethylene methyl-acrylate copolymer, ethylene ethyl-acrylate copolymer, ethylene butyl-acrylate copolymer, ethylene vinyl-acrylate copolymer and combinations thereof. Can be used.
상기 올레핀-무수말레인산 변성 공중합체는 에틸렌 부텐-무수말레인산 공중합체, 에틸렌 옥텐-무수말레인산 공중합체, 에틸렌 프로필렌-무수말레인산 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. The olefin-maleic anhydride modified copolymer may be selected from the group consisting of ethylene butene-maleic anhydride copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
상기 올레핀-무수말레인산 변성 공중합체는 주쇄 100 중량부에 대하여 무수말레인산 가지가 0.1 내지 10 중량부로 포함될 수 있으며, 구체적으로는 0.5 내지 5 중량부로 포함될 수 있다.　　무수말레인산 가지가 상기 범위 내로 포함되는 경우 기초 수지인 폴리아미드 수지와 폴리올레핀 수지의 상용성 향상 등의 물성에 유리하다. The olefin-maleic anhydride-modified copolymer may include 0.1 to 10 parts by weight of maleic anhydride with respect to 100 parts by weight of a main chain, specifically, 0.5 to 5 parts by weight. When maleic anhydride branch is contained in the said range, it is advantageous for physical properties, such as the compatibility improvement of polyamide resin and polyolefin resin which are basic resins.
상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머는 기초 수지 100 중량부에 대하여 1 내지 70 중량%로 포함될 수 있으며, 구체적으로는 15 내지 60 중량%로 포함될 수 있다. 　상기 제 2 폴리머가 상기 범위 내로 포함되는 경우 우수한 기계적 강도 및 충격 강도를 확보할 수 있을 뿐만 아니라 전도성 및 내가솔린성이 우수하다. 　특히, 상기 올레핀계 공중합체는 기초 수지 내에서 적당량으로 포함될 때, 폴리아미드 수지와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머와의 상용성이 우수하고, 올레핀계 공중합체만으로 이루어진 자체 상(phase)을 형성하지 않아 전체적으로 균일한 분산을 얻을 수 있으며, 외관이 좋다. The second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof may be included in an amount of 1 to 70 wt% based on 100 parts by weight of the base resin. It may be included in 15 to 60% by weight. When the second polymer is included in the above range, not only excellent mechanical strength and impact strength can be secured, but also excellent conductivity and resistance to gasoline. In particular, when the olefin copolymer is contained in a suitable amount in the base resin, the compatibility of the polyamide resin with a second polymer selected from the group consisting of polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin and combinations thereof It is excellent in this, and does not form its own phase which consists only of an olefin type copolymer, and can obtain uniform dispersion as a whole, and its external appearance is good.
　
(B) 카본블랙(B) carbon black
본 발명의 일 구현예에 따른 카본블랙은 케첸 블랙(ketjen black), 아세틸렌 블랙(acetylene black), 퍼니스 블랙(furnace black), 채널 블랙(channel black) 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있으며, 이 중 구체적으로는 전도성 구현이 더욱 우수한 케첸 블랙(ketjen black)을 사용할 수 있다.Carbon black according to an embodiment of the present invention may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black and combinations thereof Among them, specifically, ketjen black may be used, which is more conductive.
상기 카본블랙은 직경이 10 내지 30 nm인 입자가 전도성을 구현하기 위해서 10 ㎛의 크기로 서로 뭉쳐 있다. 　The carbon black particles 10 to 30 nm in diameter are agglomerated with each other in a size of 10 μm to implement conductivity.
상기 카본블랙은 기초 수지 100 중량부에 대하여 1 내지 15 중량부로 포함될 수 있으며, 구체적으로는 5 내지 10 중량부로 포함될 수 있다. 　카본블랙이 상기 범위 내로 포함되는 경우 전도성이 우수하고, 이로써 전도성 구현을 위한 필러의 함량을 낮출 수 있어 경제성이 좋고, 우수한 물성 구현이 용이하다. The carbon black may be included in an amount of 1 to 15 parts by weight, and specifically 5 to 10 parts by weight based on 100 parts by weight of the base resin. When the carbon black is included in the above range, the conductivity is excellent, thereby lowering the content of the filler for the conductivity can be economical, it is easy to implement excellent physical properties.
　　
(C) 탄소나노튜브(C) carbon nanotubes
본 발명의 일 구현예에 따른 탄소나노튜브는 단일벽 탄소나노튜브(single wall carbon nano-tube), 이중벽 탄소타노튜브(double wall carbon nano-tube), 다중벽 탄소나노튜브(multi wall carbon nano-tube) 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.Carbon nanotubes according to an embodiment of the present invention is a single wall carbon nanotube (single wall carbon nanotube), double wall carbon nanotube (double wall carbon nanotube), multi-wall carbon nanotube (multi wall carbon nanotube) tube) and combinations thereof.
상기 탄소나노튜브의 종횡비(튜브 길이와 지름의 비)가 클수록 공정상 분산이 어렵기 때문에, 1 내지 30 nm의 튜브 직경과 50 ㎛ 이하의 길이를 갖는 다중벽 탄소나노튜브를 사용하는 것이 좋다.　　The larger the aspect ratio (ratio of tube length and diameter) of the carbon nanotubes, the more difficult the process dispersion. Therefore, it is preferable to use multi-walled carbon nanotubes having a tube diameter of 1 to 30 nm and a length of 50 μm or less.
상기 탄소나노튜브는 기초 수지 100 중량부에 대하여 0.01 내지 5　중량부로 포함될 수 있으며, 구체적으로는 0.1 내지 1 중량부로 포함될 수 있다. 　탄소나노튜브가 상기 범위 내로 포함되는 경우 전도성 폴리아미드 복합체 조성물의 전도성을 구현하기 위한 전기적 구조(electrical percolation) 형성이 적절하고, 전도성 폴리아미드 복합체 조성물에 탄소나노튜브의 균일한 분산을 얻기 위한 공정시간이 적절하여 기초 수지의 물성, 예를 들어, 인장 강도 등의 기계적 강도와 열안정성 등을 유지할 수 있다. The carbon nanotubes may be included in an amount of 0.01 to 5 parts by weight, specifically 0.1 to 1 part by weight, based on 100 parts by weight of the base resin. In the case where the carbon nanotubes are included in the above range, it is appropriate to form an electrical percolation for realizing the conductivity of the conductive polyamide composite composition, and the process time for obtaining uniform dispersion of the carbon nanotubes in the conductive polyamide composite composition. As appropriate, the physical properties of the base resin, for example, mechanical strength such as tensile strength, thermal stability, and the like can be maintained.
본 발명의 일 구현예에 따른 전도성 폴리아미드 복합체 조성물은 카본블랙과 탄소나노튜브를 혼합 사용함으로써 전도성 필러의 양을 획기적으로 감량하였다. 　이로 인하여 상용화제 등 첨가제의 분산 효율을 향상시켰다. 　The conductive polyamide composite composition according to the embodiment of the present invention significantly reduced the amount of the conductive filler by using a mixture of carbon black and carbon nanotubes. This improved the dispersion efficiency of additives such as compatibilizers.
탄소나노튜브는 종횡비(종횡비>100)가 커서 공정 중에 분산하기 어려운 단점이 있어 용융 혼합단계에 분산 효율을 높이기 위한 고분산용 용융혼합기를 사용하여야 한다. 　Carbon nanotubes have a disadvantage in that they are difficult to disperse during the process due to their large aspect ratio (aspect ratio> 100). Therefore, a high dispersion melt mixer should be used in the melt mixing step to increase dispersion efficiency.
　
(D) 첨가제(D) additive
본 발명의 일 구현예에 따른 전도성 폴리아미드 복합체 조성물에는 첨가제로써, 수지 안정제, 가소제 등이 포함될 수 있다. 　The conductive polyamide composite composition according to the embodiment of the present invention may include a resin stabilizer, a plasticizer, or the like as an additive.
상기 수지 안정제는 예를 들어, 전도성 폴리아미드 복합체 조성물로부터 압출 또는 사출 방법을 통하여 성형품을 제조하는 과정에서, 전도성 폴리아미드 복합체 조성물에 포함된 폴리아미드 수지를 포함하는 제 1 폴리머와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머를 안정화시켜 이들 수지가 분해(예를 들어, 열분해)되거나 서로 반응하는 것을 억제하는 역할을 한다. 　이러한 수지 안정제가 포함됨에 따라, 전도성 폴리아미드 복합체 조성물 내의 폴리아미드 수지와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머가 그 자체의 특성을 보다 잘 발현할 수 있으며, 전도성 폴리아미드 복합체 조성물의 열 안정성, 성형성 등이 보다 향상될 수 있다. 　The resin stabilizer may include, for example, a first polymer comprising a polyamide resin included in the conductive polyamide composite composition, a polyolefin resin, and a polyester in the process of manufacturing a molded article from the conductive polyamide composite composition by extrusion or injection. It stabilizes a second polymer selected from the group consisting of resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers, and combinations thereof to serve to inhibit decomposition (eg, pyrolysis) or reaction of these resins with each other. As such resin stabilizers are included, a second polymer selected from the group consisting of polyamide resins, polyolefin resins, polyester resins, polyolefin-based thermoplastic elastomer resins, olefin copolymers, and combinations thereof in the conductive polyamide composite composition may be Its properties can be better expressed, and the thermal stability, moldability, etc. of the conductive polyamide composite composition can be further improved.
상기 수지 안정제로는 통상적으로 알려진 임의의 수지 안정제를 제한없이 사용할 수 있다. 　예를 들어, 상기 수지 안정제로는 인산, 트리페닐포스파이트, 트리메틸포스파이트, 트리이소데실포스파이트, 트리-(2,4-디-t-부틸페닐)포스파이트, 3,5-디-t-부틸-4-하이드록시벤질포스포닉산, 테트라키스 프로피오네이트 메탄 및 이들의 조합으로 이루어진 군에서 선택하여 사용할 수 있다. 　As the resin stabilizer, any conventionally known resin stabilizer can be used without limitation. For example, the resin stabilizer may be phosphoric acid, triphenylphosphite, trimethylphosphite, triisodecylphosphite, tri- (2,4-di-t-butylphenyl) phosphite, 3,5-di-t -Butyl-4-hydroxybenzylphosphonic acid, tetrakis propionate methane, and combinations thereof.
상기 가소제는 상기 전도성 폴리아미드 복합체 조성물의 흐름성과 성형성을 개선시킬 뿐만 아니라, 탄소나노튜브와 카본블랙의 분산을 향상시킨다. 　The plasticizer not only improves the flowability and moldability of the conductive polyamide composite composition, but also improves the dispersion of carbon nanotubes and carbon black.
상기 가소제로는 에틸렌 비스-스테아라미드(ethylene bis-stearamide), 펜타에리트리톨(pentaerythritol), 폴리카프로락톤(polycarprolactone), 고밀도 폴리에틸렌(high density polyethylene, HDPE), 캐스터 오일(caster oil), o-톨루엔 술폰아미드(ortho-toluene sulfonamide), p-톨루엔 술폰아미드(para-toluene sulfonamide)　및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The plasticizer may be ethylene bis-stearamide, pentaerythritol, polycarprolactone, high density polyethylene (HDPE), caster oil, o-toluene Ortho-toluene sulfonamide, p-toluene sulfonamide 　 And combinations thereof may be selected from the group consisting of.
　
상술한 구성 성분들을 혼합하여 전도성 폴리아미드 복합체 조성물을 제조하고, 제조된 전도성 폴리아미드 복합체 조성물을 혼합기 내에서 용융 압출하는 통상적인 방법을 통하여 성형품을 제조할 수 있다. 　The molded article may be manufactured through a conventional method of mixing the above-described components to prepare a conductive polyamide composite composition and melt extruding the prepared conductive polyamide composite composition in a mixer.
상기 전도성 폴리아미드 복합체 조성물은 60　℃에서, 20 %의 에탄올 및 연료의 침지 하에 표면 저항이 107　Ω/cm2을 유지하여 우수한 대전방지 효과를 보인다. 　또한 상기 전도성 폴리아미드 복합체 조성물은 성형성, 내화학성, 충격 특성 등의 제반 물성 우수하다. 　즉, 상기 전도성 폴리아미드 복합체 조성물은 전도성 뿐만 아니라 성형성 등의 제반 물성이 전반적으로 우수하여, 고휘발성 연료 수송 튜브에 사용할 수 있고, 또한 자동차 연료 시스템의 여러 분야에 응용될 수 있는 전도성 폴리아미드 복합체를 제공할 수 있다. The conductive polyamide composite composition is 60 　 At 占 폚, the surface resistance was maintained at 10 7 dl / cm 2 under immersion of 20% ethanol and fuel, showing an excellent antistatic effect. In addition, the conductive polyamide composite composition is excellent in various physical properties such as moldability, chemical resistance, impact properties. That is, the conductive polyamide composite composition is excellent in overall physical properties such as not only conductivity but also moldability, so that the conductive polyamide composite can be used in high volatility fuel transport tubes and can be applied to various fields of automotive fuel systems. Can be provided.
　
본 발명의 다른 일 구현예에 따르면, 상술한 전도성 폴리아미드 복합체 조성물을 이용하여 제조된 연료 수송 튜브가 제공된다. 　According to another embodiment of the present invention, there is provided a fuel transport tube made using the conductive polyamide composite composition described above.
상기 연료 수송 튜브는 폴리아미드 수지를 포함하는 제 1 폴리머와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머를 포함하는 기초 수지와 상기 기초 수지 내에 분산되어 있는 올레핀계 공중합체, 카본블랙, 탄소나노튜브 및 선택적으로 수지 안정제 및 가소제를 포함하는 형태이다. 　즉, 상기 연료 수송 튜브는 본 발명의 일 구현예에 따른 전도성 폴리아미드 복합체 조성물을 이용하여 카본블랙과 탄소나노튜브를 포함하는 성형품을 제조함으로써, 성형품 내에 부분적으로 고르게 분산되어 있는 수 마이크론 크기의 카본블랙의 사이를 탄소나노튜브가 효과적으로 연결시킴으로써 전기 전도성을 구현할 수 있다. 　또한, 이러한 플라스틱 성형품은 성형성, 열 안정성 및 내화학성 등의 제반 물성이 우수하다. 　The fuel transport tube comprises a first polymer comprising a polyamide resin and a base resin comprising a second polymer selected from the group consisting of polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins, olefin copolymers, and combinations thereof. And an olefin copolymer, carbon black, carbon nanotube, and optionally a resin stabilizer and a plasticizer dispersed in the base resin. That is, the fuel transport tube by using a conductive polyamide composite composition according to an embodiment of the present invention by producing a molded article comprising carbon black and carbon nanotubes, the carbon of several microns size is uniformly dispersed in the molded article By effectively connecting the carbon nanotubes between the black can realize electrical conductivity. In addition, these plastic molded articles have excellent physical properties such as moldability, thermal stability and chemical resistance.
이하, 실시예를 통하여 상술한 본 발명의 구현예를 보다 상세하게 설명한다. 　다만 하기의 실시예는 단지 설명의 목적을 위한 것이며 본 발명의 범위를 제한하는 것은 아니다. 　Hereinafter, embodiments of the present invention described above will be described in more detail with reference to Examples. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention.
후술하는 실시예 및 비교예에서 사용하는 (A) 기초 수지로서 (A-1) 폴리아미드 수지를 포함하는 제 1 폴리머 및 (A-2) 제 2 폴리머인 (A-2-1) 폴리올레핀 수지, (A-2-2) 폴리에스테르 수지, (A-2-3) 폴리올레핀계 열가소성 탄성체 수지 및 (A-2-4) 올레핀계 공중합체와 (B) 카본블랙 및 (C) 탄소나노튜브의 각 구성 성분의 구체적인 사양은 다음과 같다. (A-2-1) polyolefin resin which is a 1st polymer containing (A-1) polyamide resin and (A-2) 2nd polymer as (A) base resin used by the Example and comparative example which are mentioned later, (A-2-2) polyester resin, (A-2-3) polyolefin thermoplastic elastomer resin, (A-2-4) olefin copolymer, (B) carbon black and (C) carbon nanotube Specific specifications of the components are as follows.
(A) 기초 수지(A) basic resin
(A-1) 제 1 폴리머(A-1) first polymer
220 ℃에서 측정한 점도가 10,000[Pa·s](0.1[1/s] 조건) 이상인 폴리아미드 11(Arkema社의 BESNO P40TL)를 사용하였다. Polyamide 11 (BESNO P40TL, manufactured by Arkema) having a viscosity measured at 220 ° C. of 10,000 [Pa · s] (0.1 [1 / s] condition) or more was used.
(A-2) 제 2 폴리머(A-2) second polymer
(A-2-1) 폴리올레핀 수지(A-2-1) polyolefin resin
중량평균분자량(Mw)이 1,000　g/mol　이상인　선형 저밀도 폴리에틸렌(삼성토탈社의 4222F)을　사용하였다.Linear low-density polyethylene (4222F from Samsung Total) having a weight average molecular weight (Mw) of 1,000 μg / mol or more was used.
(A-2-2) 폴리에스테르 수지(A-2-2) polyester resin
폴리부틸렌 테레프탈레이트로서, 비중 1.31 g/㎤, 융점 228 ℃, 고유점도 0.83인　SHINKONG社의 Shinite K001을　사용하였다.As polybutylene terephthalate, Shinite K001 manufactured by SHINONG CORPORATION having a specific gravity of 1.31 g / cm 3, a melting point of 228 ° C., and an intrinsic viscosity of 0.83 was used.
(A-2-3)　폴리올레핀계 열가소성 탄성체 수지(A-2-3) polyolefin-based thermoplastic elastomer resin
에틸렌-프로필렌 디엔 공중합체 수지(금호석유화학의 EPDM KEP020P)를 사용하였다. Ethylene-propylene diene copolymer resin (EPDM KEP020P from Kumho Petrochemical) was used.
(A-2-4) 올레핀계 공중합체(A-2-4) Olefin Copolymer
에틸렌 부텐-무수말레인산 공중합체(DuPont社의 Fusabond MN493D)를　사용하였다.Ethylene butene-maleic anhydride copolymer (Fusabond MN493D from DuPont) was used.
(B) 카본블랙(B) carbon black
Akzo Nobel社의 ketjen black EC600JD를 사용하였다. Akzo Nobel's ketjen black EC600JD was used.
(C) 탄소나노튜브(C) carbon nanotubes
1　내지 30 nm의 튜브 직경을 갖는 다중벽 탄소나노튜브(multi wall carbon nano-tube)를 사용한다. 　다중벽 탄소나노튜브로는 Nanocyl社의 NC7000을 사용하였다. 　Multi-walled carbon nanotubes with tube diameters from 1 mm to 30 nm are used. Nanocyl NC7000 was used as the multi-walled carbon nanotube.
　
실시예 1 내지 4　및 비교예 1 내지 4Examples 1-4 ′ and Comparative Examples 1-4
상술한 각 구성 성분을 하기 표 1에 나타난 함량 범위로 각각 혼합하여 실시예 1 내지 4　및 비교예 1 내지 4의 전도성 폴리아미드 복합체 조성물을 제조하였다. 　Each of the components described above were mixed in the content ranges shown in Table 1 below to prepare the conductive polyamide composite compositions of Examples 1 to 4 ′ and Comparative Examples 1 to 4.
표 1
실시예 비교예
1 2 3 4 1 2 3 4
(A)기초수지 (A-1) 폴리아미드 11 [중량%] 63 63 63 80 63 63 63 100
(A-2) (A-2-1)　폴리올레핀 [중량%] 22 - - 20 22 22 22 -
(A-2-2) 폴리에스테르 [중량%] - 22 - - - - - -
(A-2-3) 폴리올레핀계 열가소성 탄성체 수지 [중량%] - - 22 - - - - -
(A-2-4) 올레핀계 공중합체[중량%] 15 15 15 - 15 15 15 -
(B) 카본블랙 [중량부] 6.5 6.5 6.5 6.5 - 6.5 - 6.5
(C) 탄소나노튜브 [중량부] 0.25 0.25 0.25 0.25 0.25 - - 0.25
Table 1
Example Comparative example
One 2 3 4 One 2 3 4
(A) Basic resin (A-1) Polyamide 11 [% by weight] 63 63 63 80 63 63 63 100
(A-2) (A-2-1) Polyolefin [% by weight] 22 - - 20 22 22 22 -
(A-2-2) Polyester [% by weight] - 22 - - - - - -
(A-2-3) Polyolefin thermoplastic elastomer resin [% by weight] - - 22 - - - - -
(A-2-4) Olefin Copolymer [% by weight] 15 15 15 - 15 15 15 -
(B) Carbon Black [parts by weight] 6.5 6.5 6.5 6.5 - 6.5 - 6.5
(C) carbon nanotubes [by weight] 0.25 0.25 0.25 0.25 0.25 - - 0.25
[물성 측정용 시편 제조][Production of Specimen for Measuring Property]
상기 실시예 1 내지 4 및 비교예 1 내지 4에 따른 전도성 폴리아미드 복합체 조성물을 250 ℃로 가열된 이축 용융 압출기 내에서 용융 혼련시켜 펠렛 상태로 제조하였다. 　The conductive polyamide composite compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 were melt kneaded in a twin screw melt extruder heated to 250 ° C. to prepare pellets.
이어서, 상기 펠렛을 100 ℃에서 4 시간 건조한 후, 250 ℃로 가열된 스크류식 사출기를 이용하여 굴곡강도, 인장강도 및 충격강도 등의 기계적 특성 및 전도성 평가를 위한 ASTM 시편을 제조하였다. 　Subsequently, the pellet was dried at 100 ° C. for 4 hours, and then ASTM specimens for mechanical properties and conductivity evaluation, such as flexural strength, tensile strength and impact strength, were prepared using a screw-type injection machine heated to 250 ° C.
[물성 측정 1; 기계적 강도 평가][Physical measurement 1; Mechanical strength evaluation]
플라스틱의 인장 강도를 측정하는 미국의 표준 측정 방법인 ASTM D638에 따라, 상기와 같은 방법으로 제조된 실시예 1 내지 4 및 비교예 1 내지 4의 각각의 시편에 대한 인장 강도를 측정하였고, 플라스틱의 굴곡 강도를 측정하는 미국의 표준 측정 방법인 ASTM D790에 따라, 상기와 같은 방법으로 제조된 실시예 1 내지 4 및 비교예 1 내지 4의 각각의 시편에 대한 굴곡 강도를 측정하였으며, 플라스틱의 충격 강도를 측정하는 미국의 표준 측정 방법인 ASTM D256에 따라, 상기와 같은 방법으로 제조된 실시예 1 내지 4 및 비교예 1 내지 4의 각각의 시편에 대한 충격 강도를 측정하였다. 　상기와 같이 측정한 기계적 강도를 하기 표 2에 나타내었다. 　Tensile strength was measured for each of the specimens of Examples 1 to 4 and Comparative Examples 1 to 4 prepared in the same manner as described above according to ASTM D638, a US standard measurement method for measuring the tensile strength of plastics. According to ASTM D790, a US standard measurement method for measuring flexural strength, flexural strength was measured for each of the specimens of Examples 1 to 4 and Comparative Examples 1 to 4 manufactured in the same manner as described above, and the impact strength of the plastic was measured. According to ASTM D256, which is a standard measurement method of the United States of America, the impact strength of each specimen of Examples 1 to 4 and Comparative Examples 1 to 4 prepared by the same method was measured. Mechanical strength measured as described above is shown in Table 2 below.
[물성 측정 2; 전도성 평가][Physical measurement 2; Conductivity evaluation]
상기와 같은 방법으로 제조된 실시예 1 내지 4 및 비교예 1 내지 4의 각각의 시편을 휘발유에 200 시간 침지한 후, 80 ℃에서 4시간 건조한 다음에 표면 저항을 면표면저항측정기(볼프강사 SRM-110)를 이용하여 측정하여, 그 결과를 하기 표 2에 기재하였다. 　　Each specimen of Examples 1 to 4 and Comparative Examples 1 to 4 prepared by the above method was immersed in gasoline for 200 hours, dried at 80 ° C. for 4 hours, and then the surface resistance was measured using a surface resistance meter (Wolf SRM) -110), and the results are shown in Table 2 below.
[물성 측정 3; 분산성 평가][Physical measurement 3; Dispersibility Assessment]
투과전자현미경(TEM)을 이용하여 상기 실시예 4의 시편에서 카본블랙과 탄소나노튜브의 분산성을 관찰하여 도 1에 도시하였다. 또한, 탄소나노튜브의 분산성을 비교 관찰하기 위하여 비교예 2의 시편에서 카본블랙의 분산성을 관찰하여 도 2에 도시하였다. 　The dispersion of carbon black and carbon nanotubes was observed in the specimen of Example 4 using a transmission electron microscope (TEM), and the results are shown in FIG. 1. In addition, in order to compare and observe the dispersibility of carbon nanotubes, the dispersibility of carbon black was observed in the specimen of Comparative Example 2 and shown in FIG. 2.
표 2
기계적 강도 평가 전도성 평가
인장 강도[kgf/㎠, 50 mm/min] 굴곡 강도[kgf/㎠, 2.8 mm/min] 충격 강도[kgfㆍcm/cm] 표면저항[Ω/cm2]
실시예 1 410 120 85 107
2 450 200 60 106
3 320 180 72 106
4 430 150 40 107
비교예 1 250 100 90 1012
2 370 95 95 1010
3 320 80 100 1012
4 420 250 15 1012
TABLE 2
Mechanical strength evaluation Conductivity evaluation
Tensile Strength [kgf / cm 2, 50 mm / min] Flexural Strength [kgf / ㎠, 2.8 mm / min] Impact Strength [kgf · cm / cm] Surface Resistance [Ω / cm 2 ]
Example One 410 120 85 10 7
2 450 200 60 10 6
3 320 180 72 10 6
4 430 150 40 10 7
Comparative example One 250 100 90 10 12
2 370 95 95 10 10
3 320 80 100 10 12
4 420 250 15 10 12
상기 표 2를 참조하면, 폴리아미드 수지를 포함하는 제 1 폴리머와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머에 카본블랙 및 탄소나노튜브를 본 발명의 일 구현예에 따른 범위의 양으로 용융 혼합함으로써, 전도성과 기계적 물성이 우수함을 확인하였다. 　Referring to Table 2, the carbon black in the first polymer comprising a polyamide resin and the second polymer selected from the group consisting of a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer and a combination thereof And melt mixing the carbon nanotubes in an amount in the range according to an embodiment of the present invention, it was confirmed that the conductivity and mechanical properties are excellent.
본 발명의 전도성 폴리아미드 복합체 조성물은 올레핀계 공중합체가 배합됨으로써 상용성이 높아져 충격 보강의 효과를 보였다. 　In the conductive polyamide composite composition of the present invention, the compatibility of the conductive polyamide composite is increased, and thus the impact reinforcing effect was exhibited.
첨가된 카본블랙과 탄소나노튜브는 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지　또는 올레핀계 공중합체에 비해 폴리아미드 수지와의 친화력이 우수하므로, 카본블랙과 탄소나노튜브의 대부분은 폴리아미드 수지에 분산되어 있어, 그 함량이 높지 않더라도 전도성이 구현될 수 있다.　　탄소나노튜브는 도 1에서 보듯이, 카본블랙 입자들의 사이에 전기적 다리(electrical bridge) 역할을 하여 전도성 구현을 위해 함유되는 전도성 필러의 함량을 감소시킬 수 있다. 　Since the added carbon black and carbon nanotubes have better affinity with polyamide resin than polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin or olefin copolymer, most of carbon black and carbon nanotube are polyamide resin. Dispersed in, even if the content is not high conductivity can be implemented. 　 Carbon nanotubes, as shown in Figure 1, can act as an electrical bridge (electrical bridge) between the carbon black particles to reduce the content of the conductive filler contained for the conductive implementation.
카본블랙의 분산은 비교예 2를 고배율로 확대하여 살펴보면 (도 2 참조), 카본블랙이 대부분 폴리아미드 수지에 위치하고, 특히 수지 사이의 계면에 집중적으로 모여 있으며, 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 또는 올레핀계 공중합체 상에는 거의 관찰되지 않는다. 　Dispersion of carbon black is shown by expanding the comparative example 2 to a high magnification (see FIG. 2), and most of the carbon black is located in the polyamide resin, particularly concentrated at the interface between the resins, and polyolefin resin, polyester resin, polyolefin-based It is hardly observed on the thermoplastic elastomer resin or the olefin copolymer.
상기와 같이, 본 발명의 일 구현예에 따른 전도성 폴리아미드 복합체 조성물을 적용한 성형물의 전도성은 카본블랙과 탄소나노튜브를 혼합하여 사용함으로써, 카본블랙과 탄소나노튜브가 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지　또는 올레핀계 공중합체 보다 폴리아미드 수지에 대한 높은 친화력을 가져 폴리아미드 수지의 주변에 집중적으로 위치하고, 이러한 탄소나노튜브가 카본블랙 입자들을 전기적으로 연결하여, 낮은 전도성 필러의 함량으로도 전도성을 확보할 수 있었다. 　As described above, the conductivity of the molded article to which the conductive polyamide composite composition according to one embodiment of the present invention is applied is a mixture of carbon black and carbon nanotubes, whereby carbon black and carbon nanotubes are polyolefin resins, polyester resins, and polyolefins. It has a higher affinity for a polyamide resin than a thermoplastic elastomer resin or an olefin copolymer and is concentrated in the periphery of the polyamide resin. The carbon nanotubes electrically connect the carbon black particles, so that the content of a low conductive filler The conductivity could be secured.
따라서, 상기 실시예 1 내지 4의 시편은 효과적인 카본블랙과 탄소나노튜브의 분산, 그리고 폴리아미드 수지와 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지　또는 올레핀계 공중합체와의 상용화를 통하여 인장 강도, 충격 강도 등의 기계적 물성과 전도성이 전체적으로 우수하였다. 　Accordingly, the specimens of Examples 1 to 4 exhibit tensile strength through effective dispersion of carbon black and carbon nanotubes and commercialization of polyamide resins, polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins or olefin copolymers. Mechanical properties such as impact strength and impact were excellent overall.

Claims (12)

  1. (A) (A-1) 폴리아미드 수지를 포함하는 제 1 폴리머 30 내지 99 중량% 및 (A-2) 폴리올레핀　수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 제 2 폴리머 1 내지 70 중량%를 포함하는 기초 수지 100 중량부; (A) 30 to 99% by weight of the first polymer containing (A-1) polyamide resin and (A-2) polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, olefin copolymer and combinations thereof 100 parts by weight of a base resin including 1 to 70% by weight of a second polymer selected from the group consisting of:
    (B) 카본블랙　1 내지 15 중량부; 및 (B) 1 to 15 parts by weight of carbon black; And
    (C) 탄소나노튜브 0.01 내지 5 중량부(C) 0.01 to 5 parts by weight of carbon nanotubes
    를 포함하는 전도성 폴리아미드 복합체 조성물. 　　 Conductive polyamide composite composition comprising a.
    　
  2. 제1항에 있어서, The method of claim 1,
    상기 올레핀계 공중합체는, The olefin copolymer,
    상기 폴리올레핀 수지, 폴리에스테르 수지, 폴리올레핀계 열가소성 탄성체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 수지 100 중량부에 대하여 65 내지 100 중량부로 포함되는 것인 전도성 폴리아미드 복합체 조성물. A conductive polyamide composite composition comprising 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin and combinations thereof.
    　
  3. 제1항에 있어서, The method of claim 1,
    상기 폴리아미드 수지는 폴리4-아미노부틸산(poly(4-aminobutyric acid), 폴리아미드 4); 폴리카프로락탐(polycaprolactam, 폴리아미드 6); 폴리7-아미노헵탄산(poly(7-aminoheptanoic acid), 폴리아미드 7); 폴리8-아미노옥탄산(poly(8-aminoocatanoic acid); 폴리아미드 8); 폴리9-아미노노난산(poly(9-aminononanoic acid), 폴리아미드 9); 폴리10-아미노데칸산(poly(10-aminodecanoic acid), 폴리아미드 10); 폴리(11-아미노운데칸산)(poly(11-aminoundecanoic acid), 폴리아미드 11); 폴리라우릴락탐(polylaurylactam, 폴리아미드 12); 폴리테트라메틸렌 아디프아미드(poly(tetramethylene adipamide), 폴리아미드 4,6); 폴리헥사메틸렌 아디프아미드(poly(hexamethylene adipamide), 폴리아미드 6,6); 폴리헥사메틸렌 아젤아미드(poly(hexamethylene azelamide), 폴리아미드 6,9); 폴리헥사메틸렌 세바카미드(poly(hexamethylene sebacamide), 폴리아미드 6,10); 폴리헥사메틸렌 도데카노디아미드(poly(hexamethylene dodecanodiamide), 폴리아미드 6,12); 폴리헵타메틸렌 피멜아미드(poly(heptamethylene pimelamide), 폴리아미드 7,7); 폴리옥타메틸렌 수베라미드(poly(octamethylene suberamide), 폴리아미드 8,8); 폴리노나메틸렌 아젤아미드(poly(nonamethylene azelamide), 폴리아미드 9,9); 폴리데카메틸렌 아젤아미드(poly(decamethylene azelamide), 폴리아미드 10,9); 폴리아미드 6/6,10 공중합체; 폴리아미드 6/6,6 공중합체; 폴리아미드 6/12 공중합체; 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The polyamide resin may be poly4-aminobutyl acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene dodecanodiamide (poly (hexamethylene dodecanodiamide), polyamide 6,12); Polyheptamethylene pimelamide (poly (heptamethylene pimelamide), polyamide 7,7); Polyoctamethylene subberamide (poly (octamethylene suberamide), polyamide 8,8); Poly (nonamethylene azelamide), polyamide 9,9; Polydecamethylene azelamide (polyamide 10,9); Polyamide 6 / 6,10 copolymer; Polyamide 6 / 6,6 copolymer; Polyamide 6/12 copolymer; And a combination thereof.
    　
  4. 제1항에 있어서,The method of claim 1,
    상기 폴리올레핀 수지는 0.94 kg/m3 내지 0.965 kg/m3의 밀도를 갖는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 0.91 kg/m3 내지 0.94 kg/m3의 밀도를 갖는 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 폴리프로필렌, 에틸렌-비닐알코올 공중합체, 에틸렌-프로필렌 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The polyolefin resin is a high density polyethylene (HDPE) having a density of 0.94 kg / m 3 to 0.965 kg / m 3 , linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene, LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer, and combinations thereof.
    　
  5. 제1항에 있어서,The method of claim 1,
    상기 폴리에스테르 수지는 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리헥사메틸렌 테레프탈레이트 수지, 폴리시클로헥산 디메틸렌 테레프탈레이트 수지, 이들 수지에 일부 다른 단량체를 혼합하여 비결정성으로 개질한 수지 및 이들의 조합으로 이루어진 군에서 선택되는　것인 전도성 폴리아미드 복합체 조성물. 　　The polyester resin may be prepared by mixing polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, and some other monomers in these resins. A conductive polyamide composite composition selected from the group consisting of qualitatively modified resins and combinations thereof.
    　
  6. 제1항에 있어서, The method of claim 1,
    상기 폴리올레핀계 열가소성 탄성체 수지는 에틸렌-프로필렌 디엔 공중합체 수지(EPDM), 에틸렌-프로필렌 고무(EPR) 및 이들의　조합으로 이루어진 군에서 선택되는　것인 전도성 폴리아미드 복합체 조성물. 　　The polyolefin-based thermoplastic elastomer resin is selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR) and a combination of these conductive polyamide composite composition.
    　
  7. 제1항에 있어서, The method of claim 1,
    상기 올레핀계 공중합체는 올레핀-아크릴레이트 공중합체, 올레핀-무수말레인산 변성 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The olefin-based copolymer is selected from the group consisting of olefin-acrylate copolymer, olefin-maleic anhydride modified copolymer, and combinations thereof.
    　
  8. 제7항에 있어서, The method of claim 7, wherein
    상기 올레핀-아크릴레이트 공중합체는 에틸렌 메틸-아크릴레이트 공중합체, 에틸렌 에틸-아크릴레이트 공중합체, 에틸렌 부틸-아크릴레이트 공중합체, 에틸렌 비닐-아크릴레이트 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The olefin-acrylate copolymer is selected from the group consisting of ethylene methyl-acrylate copolymer, ethylene ethyl-acrylate copolymer, ethylene butyl-acrylate copolymer, ethylene vinyl-acrylate copolymer and combinations thereof. Phosphorus Conductive Polyamide Composite Composition.
    　
  9. 제7항에 있어서, The method of claim 7, wherein
    상기 올레핀-무수말레인산 변성 공중합체는 에틸렌 부텐-무수말레인산 공중합체, 에틸렌 옥텐-무수말레인산 공중합체, 에틸렌 프로필렌-무수말레인산 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The olefin-maleic anhydride modified copolymer is selected from the group consisting of ethylene butene-maleic anhydride copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
    　
  10. 제1항에 있어서, The method of claim 1,
    상기 카본블랙은 케첸 블랙(ketjen black), 아세틸렌 블랙(acetylene black), 퍼니스 블랙(furnace black), 채널 블랙(channel black) 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　Wherein the carbon black is selected from the group consisting of ketjen black, acetylene black, furnace black, channel black, and combinations thereof.
    　
  11. 제1항에 있어서, The method of claim 1,
    상기 탄소나노튜브는 단일벽 탄소나노튜브(single wall carbon nano-tube), 이중벽 탄소나노튜브(double wall carbon nano-tube), 다중벽 탄소나노튜브(multi wall carbon nano-tube) 및 이들의 조합으로 이루어진 군에서 선택되는 것인 전도성 폴리아미드 복합체 조성물. 　The carbon nanotubes are single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes, and combinations thereof. Conductive polyamide composite composition is selected from the group consisting of.
  12. 제1항 내지 제11항 중 어느 한 항에 따른 전도성 폴리아미드 복합체 조성물을 이용하여 제조된　연료 수송 튜브. A fuel transport tube made using the conductive polyamide composite composition according to any one of claims 1 to 11.
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