WO2018025824A1 - Composition de résine conductrice - Google Patents

Composition de résine conductrice Download PDF

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Publication number
WO2018025824A1
WO2018025824A1 PCT/JP2017/027785 JP2017027785W WO2018025824A1 WO 2018025824 A1 WO2018025824 A1 WO 2018025824A1 JP 2017027785 W JP2017027785 W JP 2017027785W WO 2018025824 A1 WO2018025824 A1 WO 2018025824A1
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Prior art keywords
resin
component
mass
content
resin composition
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PCT/JP2017/027785
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English (en)
Japanese (ja)
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秀臣 片野
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片野染革株式会社
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Publication of WO2018025824A1 publication Critical patent/WO2018025824A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a thermoplastic conductive resin composition using carbon nanotubes.
  • a conductive material imparted with conductivity by adding a carbon material to a thermoplastic resin and a resin product using the conductive material are widely used.
  • carbon materials it is well known that carbon nanotubes have a smaller tube diameter (or fiber diameter) and a larger aspect ratio than other carbon materials, so that conductivity can be obtained at a low concentration.
  • carbon nanotubes supplied as raw materials that is, raw materials
  • carbon black and graphite are often used as a conductive material added to a resin, partly because dispersion is easier to control than carbon nanotubes.
  • control of dispersion in the resin has become a major issue.
  • the carbon nanotubes are mixed with a propylene-olefin copolymer wax to form a master batch, which is a thermoplastic polycondensate, styrene polymer, polyamide, polyester, polycarbonate, polyacrylate, polyacrylate copolymer, polyacetal, polyolefin, polyolefin copolymer,
  • a conductive material obtained by mixing with an organic polymer selected from the group consisting of these substances and a mixture of these substances has been proposed (Claims of Patent Document 2, etc.).
  • the master batch is more easily prepared than the conventional carbon nanotube master batch in a high molecular weight polymer (Claims of Patent Document 3, paragraph 0006, etc.).
  • a method for improving the melt flow characteristics of the conductive thermoplastic composition by using a carbon nanotube masterbatch in wax is also desirable.
  • the thermoplastic resin is polyester, poly (vinyl chloride), polystyrene, Rubber-modified polystyrene, polyolefin, polycarbonate, polyimide, polyetherimide, poly (ether ketone), poly (ether ether ketone), polysulfone, poly (arylene ether), poly (phenylene sulfide), polyamide, copolymer of styrene and acrylonitrile, copolymer of ⁇ -methylstyrene and acrylonitrile, copolymer of acrylonitrile, butadiene and styrene, copolymer of acrylonitrile, styrene and acrylate ester, polyacetal, It is selected from the group consisting of thermoplastic polyurethane, and combinations thereof (the 0001 paragraph of Patent Document 3, claim 11, or the like).
  • the inventor of the present invention uses a carbon nanotube, an olefin polymer satisfying the following (1) to (3), and a resin composition including a thermoplastic resin to have a high conductivity with a volume resistivity in the thickness direction of 100 ⁇ ⁇ cm or less.
  • a functional resin composition is proposed.
  • This conductive resin composition contains 15 to 40% by mass of carbon nanotubes, and the olefin polymer has (1) a weight average molecular weight (Mw) of 35,000 to 150,000, and (2) a molecular weight distribution ( Mw / Mn) is 3 or less, and (3) the softening point is 80 to 130 ° C. (Claim 1, Paragraph 0053, etc. of Patent Document 4).
  • JP 2008-290936 A Special table 2012-507588 gazette Special table 2014-511908 gazette Japanese Unexamined Patent Publication No. 2016-41806
  • a dry color is prepared by mixing the pigment with metal soap, wax, plasticizer, etc., and melted and kneaded with the base resin.
  • a method for improving dispersibility is a well-known technique.
  • a masterbatch technique is also widely used in which a resin that is compatible with both the pigment and the base resin is selected, the pigment is masterbatched at a high concentration, and the pigment is easily dispersed in the base resin.
  • pigment dispersion techniques can be used as a reference when dispersing carbon nanotubes, but cannot be used directly for dispersing carbon nanotubes.
  • the carbon nanotubes are mixed with a plasticizer or a wax to make the carbon nanotubes easy to disperse. It is improving.
  • a plasticizer or a wax to make the carbon nanotubes easy to disperse. It is improving.
  • a large amount of plasticizer, wax, and the like are required per unit mass as compared with existing materials such as pigments.
  • plasticizers and waxes are added to improve dispersibility, the performance of the base resin is adversely affected by bleedout of these components or deterioration of mechanical properties. Yes.
  • the inventor has developed a volume resistivity in the thickness direction by carbon nanotubes, an olefin polymer satisfying the following (1) to (3), and a thermoplastic resin.
  • a conductive resin composition having a high resistance of 100 ⁇ ⁇ cm or less.
  • the carbon nanotubes are contained in an amount of 15 to 40% by mass.
  • this olefin polymer which is not a plasticizer or wax, has (1) a weight average molecular weight (Mw) of 35,000 to 150,000, (2) a molecular weight distribution (Mw / Mn) of 3 or less, (3 )
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • the softening point is 80 to 130 ° C., the molecular weight is larger than that of plasticizers and waxes, and adverse effects on the performance of the base resin are reduced due to bleeding out and mechanical properties.
  • the inventors have found a production method in which the olefin polymer is stirred with carbon nanotubes at a temperature of 90 ° C. or more and a stirring speed of 300 rpm or more to obtain a mixture, and then melt-mixed with a thermoplastic resin to obtain a resin composition.
  • Patent Document 4 is mainly intended for high conductivity fields such as a bipolar plate of a redox flow battery and a separator of a fuel cell, and the volume resistivity in the thickness direction is 100 ⁇ ⁇ cm or less.
  • the content of carbon nanotubes is as large as 15 to 40% by mass.
  • the present invention is directed to the conductive field such as so-called antistatic, and an object thereof is to provide a conductive resin composition having a volume resistivity of 10 ⁇ ⁇ cm or more in the surface direction.
  • olefin polymer having a specific physical property value (hereinafter, also simply referred to as “olefin polymer”) and a carbon nanotube. It was found that can be solved.
  • This olefin polymer has less bleed-out from the base resin and less softening the base resin than plasticizers and waxes.
  • the present invention provides the following [1] to [4].
  • [1] (A) carbon nanotube, (B) (1) The weight average molecular weight (Mw) is 35,000 to 150,000, (2) the molecular weight distribution (Mw / Mn) is 3 or less, and (3) the softening point is 80 to 130 ° C.
  • the content of component (A) is 1 to 14% by mass with respect to the total of 100% by mass of (A) to (C), and the content of component (B) is the content of component (A).
  • the conductive resin composition is characterized by being 0.5 to 2 times the mass of the conductive resin composition.
  • An olefin polymer (C) a thermoplastic resin, and (D) a non-conductive inorganic filler
  • the content of the component (A) is 0.5 to 4.9% by mass with respect to the total of 100% by mass of the components (A) to (D)
  • the content of the component (B) is (A)
  • the content of the component is 0.5 to 2 mass times, and the content of the component (D) is 6 to 40 mass% with respect to a total of 100 mass% of the components (A) to (D).
  • a conductive resin composition characterized by the above.
  • Component (C) is polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyvinyl chloride resin, polymethylpentene resin, syndiotactic polystyrene resin, polyacetal resin, polyamide resin, polycarbonate resin, poly Selected from butylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polyphenylene sulfide resin, polyamideimide resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, liquid crystal resin, and aromatic polyimide resin
  • [4] A molded article using a cured product of the conductive resin composition according to any one of [1] to [3].
  • the conductive resin composition containing carbon nanotubes according to the present invention [1] or [2] can be obtained with a lower carbon nanotube content than carbon black and graphite, this conductive resin composition can be obtained. Excellent in moldability and mechanical properties of the resin used.
  • ⁇ First Aspect of Conductive Resin Composition of the Present Invention> As a 1st aspect of the conductive resin composition of this invention, (A) a carbon nanotube, (B) (1) The weight average molecular weight (Mw) is 35,000 to 150,000, (2) the molecular weight distribution (Mw / Mn) is 3 or less, and (3) the softening point is 80 to 130 ° C. An olefin polymer, and (C) a thermoplastic resin, The content of component (A) is 1 to 14% by mass with respect to the total of 100% by mass of (A) to (C), and the content of component (B) is the content of component (A). 0.5 to 2 times the mass.
  • At least three components (A), (B), and (C) are included. Since the content ratio of the component (A), the component (B), and the component (C) affects the conductivity and mechanical strength, the content of the three components is adjusted to balance these components.
  • the content of the component (A) is 1 to 14% by mass, preferably 2 to 10% by mass, more preferably 3 to 8% by mass with respect to 100% by mass of the total of the components (A) to (C). It is. When the content of the component (A) is less than 1% by mass, conductivity may not be exhibited. On the other hand, when the content of the component (A) exceeds 14% by mass, the electrical conductivity increases, but the content of the component (C) decreases, so that the mechanical properties may be inferior.
  • the content of the component (B) is 0.5 to 2 times, preferably 0.7 to 1.8 times, more preferably 1.0 to 1.8 times the content of the component (A). Is double. If content of (B) component is less than 0.5 time, the dispersibility of (A) component will worsen and there exists a possibility of reducing electroconductivity. Moreover, when the content of the component (B) exceeds twice, the molded product tends to be soft.
  • the content of the component (C) is the remainder obtained by subtracting the contents of the components (A) and (B) from the total 100% by mass of the components (A) to (C). Therefore, when the content of the component (A) and the component (B) increases, the content of the component (C) relatively decreases.
  • the carbon nanotube of component (A) used in the present invention is a cylindrical hollow fiber material made of carbon, and its structure may be a single layer or a multilayer, but it is easy to disperse. From the viewpoint, a multilayer structure is preferable.
  • any commercially available product can be used, but those having an average diameter (average thickness) of 5 to 20 nm and an average length of about 0.5 to 50 ⁇ m are used. Easy and preferable. If the average diameter of the carbon nanotubes is 5 nm or more, the carbon nanotubes can be hardly cut at the time of kneading, and if it is 20 nm or less, the conductivity can be increased. In addition, if the average length of the carbon nanotube is 0.5 ⁇ m or more, the conductivity can be increased, and if it is 50 ⁇ m or less, an increase in viscosity during kneading can be suppressed and kneading and molding can be facilitated.
  • the average diameter of the carbon nanotubes is more preferably 6 to 20 nm, still more preferably 7 to 20 nm, and the average length is more preferably 0.5 to 30 ⁇ m, still more preferably 0.6 to 15 ⁇ m.
  • the said average long diameter and average length can be calculated
  • required by observing a carbon nanotube with an electron microscope (SEM, TEM), and carrying out arithmetic average (n 50).
  • the carbon nanotube as component (A) can be produced by an arc discharge method, a chemical vapor deposition method (CVD method), a laser ablation method, or the like.
  • the carbon nanotube as the component (A) a known carbon nanotube can be used.
  • Examples of commercially available products include multi-walled carbon nanotubes such as Flo Tube 9000 from C-Nano Technology, C-100 from Arkema, NC7000 from Nanocyl. These commercial products satisfy the above-mentioned average major axis and average length, and can be preferably used. It is also excellent in terms of starting mass production and price competitiveness.
  • the (B) component olefin polymer used in the present invention satisfies the following (1) to (3).
  • Mw / Mn Molecular weight distribution
  • Softening point 80-130 ° C
  • an olefin polymer obtained by polymerizing at least one monomer selected from ethylene and an ⁇ -olefin having 3 to 28 carbon atoms is preferable.
  • Examples of the ⁇ -olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1- Examples include dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-icocene.
  • ⁇ -olefins having 3 to 24 carbon atoms are preferable, ⁇ -olefins having 3 to 12 carbon atoms are more preferable, ⁇ -olefins having 3 to 6 carbon atoms are more preferable, and 3 to 4 carbon atoms are particularly preferable.
  • olefin polymer of the component (B) an olefin homopolymer obtained by polymerizing one of these alone may be used, or an olefin polymer obtained by copolymerizing two or more of them in combination. A copolymer may be used.
  • olefin polymer includes both olefin homopolymers and olefin copolymers.
  • examples thereof include a system polymer (1) and a butene polymer in which 50 mol% or more of monomers constituting the polymer is a butene monomer. From the viewpoint of heat resistance and mechanical strength, the propylene polymer (1) is preferred.
  • propylene polymer (1) examples include propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene- ⁇ -olefin block copolymer, propylene-ethylene random copolymer, propylene It is preferably a propylene-based polymer selected from a butene random copolymer, a propylene- ⁇ -olefin random copolymer, a propylene- ⁇ -olefin graft copolymer, etc., particularly from the viewpoint of mechanical strength Propylene homopolymer is preferred.
  • the content of the structural unit of the ⁇ -olefin having 3 carbon atoms is preferably 50 mol% or more, more preferably 65 mol% of the monomer constituting the polymer. % Or more, more preferably 75 mol% or more, still more preferably 80 mol% or more.
  • a propylene polymer (2) satisfying at least one of the following (i) and (ii) can also be used.
  • a structural unit of ethylene is contained in an amount of more than 0 mol% and 25 mol% or less.
  • the structural unit of 1-butene is contained in an amount of more than 0 mol% to 30 mol%.
  • the propylene polymer (2) is a copolymer containing an olefin having 2 carbon atoms (that is, an ethylene monomer)
  • the content of the constituent unit of the olefin having 2 carbon atoms constitutes the polymer.
  • the monomer is preferably more than 0 mol% and 25 mol% or less, more preferably more than 0 mol% and 23 mol% or less, still more preferably more than 0 mol% and 20 mol% or less, still more preferably more than 0 mol%. 18 mol% or less.
  • the content of the 1-butene constituent unit is preferably that of the monomer constituting the polymer. It is more than 0 mol% and 30 mol% or less, more preferably more than 0 mol% and 27 mol% or less, still more preferably more than 0 mol% and 20 mol% or less.
  • the component (B) olefin polymer has a weight average molecular weight (Mw) of 35,000 to 150,000, a molecular weight distribution (Mw / Mn) of 3 or less, and a softening point of 80 to 130 ° C.
  • Polymers called so-called waxes such as propylene-based polymers and ethylene-based polymers having a weight average molecular weight (Mw) of less than 35,000 have an influence on product properties due to heat resistance and bleed out, and use is restricted. .
  • the weight average molecular weight (Mw) is preferably 40,000 to 140,000, more preferably 42,000 to 130,000.
  • the molecular weight distribution (Mw / Mn) is preferably 2.8 or less, more preferably 2.5 or less.
  • the dispersibility of the component (A) can be improved and the processing temperature can be lowered.
  • the softening point is preferably 90 to 125 ° C, more preferably 93 to 120 ° C.
  • an olefin polymer synthesized with a metallocene catalyst is suitable.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) method to obtain the molecular weight distribution (Mw / Mn).
  • GPC gel permeation chromatography
  • the following apparatus and conditions are used for a measurement, and the weight average molecular weight and number average molecular weight of polystyrene conversion are obtained.
  • the molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
  • thermoplastic resin of component (C) used in the present invention examples include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyvinyl chloride resin, polymethylpentene resin, syndiotactic polystyrene resin, and polyacetal resin.
  • Polyamide resin, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polyphenylene sulfide resin, polyamideimide resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, liquid crystal resin, and aromatic A polyimide resin etc. are mentioned. In addition, these may be used individually by 1 type, or may be used in combination of 2 or more type.
  • An olefin polymer (C) a thermoplastic resin, and (D) a non-conductive inorganic filler
  • the content of the component (A) is 0.5 to 4.9% by mass with respect to the total of 100% by mass of the components (A) to (D)
  • the content of the component (B) is (A)
  • the content of the component is 0.5 to 2 mass times, and the content of the component (D) is 6 to 40 mass% with respect to 100 mass% of the total of the components (A) to (D).
  • the present inventor further comprises (D) a non-conductive inorganic filler as component (D) in the conductive resin composition based on the conductive resin composition of the first aspect. It has been found that even when the content of the component carbon nanotubes is reduced, conductivity is exhibited.
  • At least four components of (A) component, (B) component, (C) component, and (D) component are included. Since the content ratio of the component (A), the component (B), the component (C), and the component (D) affects the electrical conductivity and mechanical properties, the content of the above four components should be balanced. Adjust.
  • the content of component (A) is 0.5 to 4.9% by mass, preferably 0.8 to 4.5% by mass, based on 100% by mass of the total of components (A) to (C).
  • the amount is preferably 1 to 4% by mass.
  • content of the component (A) is less than 0.5% by mass, conductivity may not be exhibited.
  • content of (A) component exceeds 4.9 mass%, although electroconductivity will become high, since content of (C) component decreases, there exists a possibility that it may be inferior to mechanical strength.
  • the content of the component (B) is 0.5 to 2 times, preferably 0.7 to 1.8 times, more preferably 1.0 to 1.8 times the content of the component (A). Is double. If content of (B) component is less than 0.5 mass times, the dispersibility of (A) component will worsen and there exists a possibility of reducing electroconductivity. Moreover, when content of (B) component exceeds 2 mass times, it will become the tendency for a molded article to become soft.
  • the content of component (D) is 6 to 40% by mass, preferably 8 to 38% by mass, more preferably 10 to 35% by mass, with respect to 100% by mass of the total of components (A) to (D). is there. If the content of the component D) is less than 6% by mass, the conductivity may be lowered, and if the content of the component D) exceeds 40% by mass, the mechanical properties may be deteriorated.
  • the content of the component (C) is the remainder obtained by subtracting the contents of the components (A), (B), and (D) from the total 100% by mass of the components (A) to (D).
  • the content of the component (C) relative to the total of 100% by mass of the components (A) to (D) is preferably as much as possible in order to maintain the characteristics as the base resin, preferably 50% by mass or more, more preferably Is 55% by mass or more, more preferably 60% by mass or more.
  • Non-conductive inorganic filler examples include calcium carbonate, precipitated barium sulfate, talc, diatomaceous earth, mica, glass, alumina, magnesium carbonate, calcium sulfate and the like. Of these, calcium carbonate, precipitated barium sulfate, and talc, which have established techniques for addition to resins and are price competitive, are preferable.
  • As a shape of a component commercially available things, such as granular shape, needle shape, and flake shape, can be used. These non-conductive inorganic fillers may be subjected to surface treatment for the purpose of improving the dispersibility in the resin. In addition, these may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the average particle diameter of the component (D) is preferably 0.3 to 50 ⁇ m, more preferably 0.5 to 20 ⁇ m, still more preferably 0.5 to 10 ⁇ m, from the viewpoint of easy addition.
  • the average particle diameter means a 50% average particle diameter, and is determined using, for example, a Microtrac particle size analyzer (dynamic light scattering method) manufactured by Nikkiso Co., Ltd.
  • the component (D) is a process in which the resin component composed of the component (B) and the component (C) is solidified, and the component (A) is collected on the surface of the component (D), It is considered that the effect of suppressing aggregation and efficiently performing electrical connection between the components (A) can be obtained. Therefore, by including the component (D) in the resin composition, the conductivity can be increased even if the content of the component (A) is reduced.
  • the conductive resin composition of the present invention is a lubricant, antistatic agent, ultraviolet absorber, pigment, and the like generally contained in this type of composition as long as the effects of the present invention are not impaired. Additives such as organic fillers can be contained as necessary. The same applies to the conductive resin composition of the first aspect described above.
  • an example of the production method of the first aspect of the conductive resin composition of the present invention is to stir the components (A) and (B) at a temperature of 90 ° C. or more and a stirring speed of 300 rpm or more to obtain a mixture. Then, the mixture is added to the component (C) to obtain a resin composition.
  • an example of the manufacturing method of the 2nd aspect of the conductive resin composition of this invention is (A) component and (B) component are stirred at the temperature of 90 degreeC or more and the stirring speed of 300 rpm or more, and a mixture is obtained. Then, the mixture is added to the component (C) and the component (D) to obtain a conductive resin composition.
  • (A) component and (B) component are thrown into a mixer, and (B) component is softened.
  • the component (A) is loosened and the component (B) adheres to the surface of the component (A).
  • the component (B) adheres to the surface of the component (A), and this causes the component (A) to easily mix with the component (C) during melt kneading with the component (C).
  • High dispersion of the component (A) to the component (C) is enabled.
  • the stirring temperature is preferably 100 to 180 ° C., more preferably 120 to 160 ° C.
  • the stirring speed is preferably 400 to 3000 rpm, more preferably 500 to 2500 rpm.
  • the stirring time is not particularly limited as long as the component (A) and the component (B) are sufficiently stirred and mixed, but it is preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours.
  • a mixer for stirring and mixing for example, a known high-speed stirring mixer such as a dissolver, butterfly mixer, paddle blade mixer, Henschel mixer, super mixer, Banbury mixer, kneader, and trimix can be used. Specifically, an FM mixer manufactured by Nippon Coke Kogyo Co., Ltd., a super mixer manufactured by Kawata Co., Ltd., and the like can be given.
  • the total amount of component (A) and the total amount of component (B) may be mixed in one shot, but after the total amount of component (A) and a part of component (B) are mixed, the remainder Multi-stages such as a method of further adding and mixing the component (B), a method of mixing a part of the component (A) and the total amount of the component (B), and further adding and mixing the remaining component (A) May be mixed.
  • the obtained mixture (powder mixture) is added to the component (C) and mixed.
  • the obtained mixture (powder mixture) is added to (C) component and (D) component and mixed.
  • the mixture of the above mixture (powder mixture), the component (C) and the component (D) is melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, and granulated into pellets, thereby forming a conductive resin composition.
  • the heating temperature in melt kneading is preferably 150 to 600 ° C., more preferably 200 to 500 ° C.
  • the above mixture (powder mixture) and a part of the component (C) are melt-kneaded with a single screw or twin screw extruder, extruded into a strand shape, granulated into pellets, and the remaining (C A so-called master batch method may be used in which the components are mixed, melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, and granulated into pellets.
  • the conductive resin composition can be provided to a molding process such as injection molding by pellet blending with the component (C).
  • the carbon nanotube of the component (A) can be highly dispersed in the resin, so that the conductive resin composition that can be molded with excellent conductivity and mechanical properties with a small addition amount. It can be a thing.
  • the above-described manufacturing method is simple and excellent in cost reduction.
  • the melt flow rate (MFR) of the resin composition of the first aspect or the second aspect obtained by the above production method is preferably 0.1 to 100 g / 10 min, more preferably 0.3 to 50 g / 10 min. is there.
  • the volume resistivity of the molded product of the resin composition of the first aspect or the second aspect is preferably 1 ⁇ 10 7 to 1 ⁇ 10 1 ⁇ ⁇ cm, more preferably 1 ⁇ 10 6 to 2 ⁇ 10. 1 ⁇ ⁇ cm.
  • the flexural modulus of the cured product of the resin composition is preferably 200 MPa or more, more preferably 300 MPa or more, and even more preferably 400 MPa or more.
  • the Charpy impact strength of the cured product of the resin composition is preferably 0.5 kJ / m 2 or more, more preferably 0.7 kJ / m 2 or more, and further preferably 1.0 kJ / m 2 or more.
  • each physical property value can be specifically measured by the method described in the examples.
  • a molded body using the conductive resin composition of the present invention can be usually produced by various molding methods employed for thermoplastic resins. Examples of the manufacturing method include an injection molding method, an extrusion molding method, a calendar molding method, a press molding method, and the like.
  • a bending test and a Charpy impact test sample were prepared using an injection molding machine (Toshiba Machine Co., Ltd., IS80EPN-2A) and a test piece molding die (clamping force: 80 t) compliant with JIS K6911.
  • the cylinder set temperature during molding was 200 to 300 ° C.
  • MFR Melt flow rate According to JIS K7210, it was measured by a melt indexer (manufactured by Toyo Seiki Seisakusho, P-01 type). The measurement temperatures and loads are shown in Tables 1 to 4.
  • Bleed property evaluation The bleed property from the conductive resin composition of an olefin polymer, a plasticizer, and a wax was evaluated by the following method. A sheet of 10 cm ⁇ 10 cm and 3 mm thickness obtained by press-molding the conductive resin composition in the form of pellets at a temperature 20 ° C. lower than the MFR measurement temperature is placed in a constant temperature bath at 120 ° C. for 12 hours, and the gloss of the surface The change was visually evaluated to determine bleeding.
  • the evaluation scales were as follows: ⁇ : no change, ⁇ : slightly cloudy, x: fairly cloudy.
  • each component used in the examples and comparative examples is as follows.
  • C-2) “Neozex C4-LLDPE 45200” (polyethylene resin) manufactured by Prime Polymer Co., Ltd.
  • C-3) “Nylon resin injection 1013B” (polyamide resin) manufactured by Ube Industries, Ltd.
  • C-4) “Novaduran 5010CR2” (polybutylene terephthalate resin) manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • D-2) “MICRO ACE P-3” (talc) average particle diameter 5.0 ⁇ m, manufactured by Nippon Talc Co., Ltd.
  • a die with a hole for taking out a strand having a diameter of 3 mm was attached to the outlet of the biaxial kneader, the kneaded product was extruded from the die, put into a water tank, cooled, and pelletized with a strand cutter.
  • Tables 1 and 2 show physical property evaluations of the obtained pellets. In Tables 1 and 2, a blank represents no inclusion.
  • component (A), component (C), and component (E) shown in Table 2 were dry blended and twin screw extruder (Toshiba Machine Co., Ltd., TEM-35B [screw diameter: 35 mm, L / D: 32, vent type]), and melt kneading at a stirring rotation speed of 100 rpm and a kneading temperature of MFR measurement temperature + 30 ° C. shown in Table 2.
  • a die with a hole for taking out a strand having a diameter of 3 mm was attached to the outlet of the biaxial kneader, the kneaded product was extruded from the die, put into a water tank, cooled, and pelletized with a strand cutter.
  • Table 2 shows the physical property evaluation of the obtained pellets.
  • Examples 1 to 6 were good results in all of MFR, volume resistivity, flexural modulus, Charpy impact value, and bleed property evaluation.
  • Comparative Example 1 had a high volume resistivity and a low flexural modulus and Charpy impact value.
  • the volume resistivity was high, the flexural modulus was low, and the bleeding property evaluation was bad.
  • the flexural modulus was low and the bleedability evaluation was poor.
  • Comparative Example 4 the flexural modulus and Charpy impact value were low, and the bleeding property evaluation was poor.
  • Comparative Example 5 the bleeding property evaluation was bad.
  • Comparative Examples 2 to 5 obtain a low volume resistivity.
  • Comparative Examples 4 to 5 via the preparation of the powdery mixture have considerably good volume resistivity, and it can be said that the preparation of the powdery mixture is an effective means even in the comparative example.
  • Comparative Examples 1-2 are inferior.
  • the dispersion state of the carbon nanotubes and the contact state of the carbon nanotubes for electrical conductivity act in a complicated relationship with the polyolefin polymer and the thermoplastic resin, but the details About is unknown.
  • Comparative Example 1 only carbon nanotubes were added to the resin without adding a dispersion aid, and the volume resistivity was 1 ⁇ 10 6 ⁇ ⁇ cm or more, which was a result of no practicality. .
  • a die with a hole for taking out a strand having a diameter of 3 mm was attached to the outlet of the biaxial kneader, the kneaded product was extruded from the die, put into a water tank, cooled, and pelletized with a strand cutter.
  • Tables 3 to 4 show physical property evaluations of the obtained pellets. In Tables 3 to 4, a blank represents no inclusion.
  • Comparative Example 6 The contents of component (A), component (C), component (D), and component (E) shown in Table 4 were dry blended and a twin screw extruder (Toshiba Machine Co., Ltd., TEM-35B [Screw Diameter: 35 mm, L / D: 32, bent type]), and melt kneading at a stirring rotation speed of 100 rpm and a kneading temperature of MFR measurement temperature + 30 ° C. shown in Table 2.
  • a twin screw extruder Toshiba Machine Co., Ltd., TEM-35B [Screw Diameter: 35 mm, L / D: 32, bent type]
  • a die with a hole for taking out a strand having a diameter of 3 mm was attached to the outlet of the biaxial kneader, the kneaded product was extruded from the die, put into a water tank, cooled, and pelletized with a strand cutter.
  • Table 4 shows the physical property evaluation of the obtained pellets.
  • Examples 7 to 11 had good results in all of MFR, volume resistivity, flexural modulus, Charpy impact value, and bleed property evaluation.
  • Comparative Example 6 had a high volume resistivity and poor bleedability evaluation.
  • Comparative Example 7 and Comparative Example 8 had poor bleedability evaluation.
  • Comparative Examples 7 to 8 through the preparation of the powder mixture had a fairly good volume resistivity, and the preparation of the powder mixture was also effective in Comparative Examples 7 to 8. It can be said that means. However, Comparative Example 8 is inferior to Examples 7-12.
  • Example 3 and Example 9 contain the carbon nanotubes as component (A). Although the amount is the same, the second embodiment containing the non-conductive inorganic filler of the component (D) can exhibit higher conductivity.
  • the component (A) in the process of solidifying the resin component composed of the component (B) and the component (C) by containing the component (D). Are gathered on the surface of the component (D), thereby suppressing the aggregation of the component (A), and the electrical connection between the carbon nanotubes of the component (A) is efficiently performed.
  • any product that can add a non-conductive inorganic filler can be an effective means.
  • the dispersion of the carbon nanotubes and the contact state of the carbon nanotubes for electrical conduction are mutually connected to the polyolefin polymer, the thermoplastic resin, and the non-conductive inorganic filler. It can be inferred that they are working closely, but the detailed mechanism is unknown.
  • the molded body composed of the conductive resin composition composed of the carbon nanotubes of the present invention can obtain conductivity with a low amount of carbon nanotubes compared to carbon black and graphite, the moldability of the base resin, and It has excellent mechanical properties and is suitable for injection molded products, extrusion molded products, films, and sheets that require antistatic properties.

Abstract

L'invention a pour objet de fournir une composition de résine conductrice qui peut être mise en œuvre dans les domaines de la conduction électrique tels que la prévention de charge électrostatique, et qui présente une résistivité volumique dans une direction de plan supérieure ou égale à １０Ω・ｃｍ. Plus précisément, l'invention concerne une composition de résine conductrice qui est caractéristique en ce qu'elle contient : (A) des nanotubes de carbone ; (B) un polymère à base d'oléfine qui présente (1) une masse moléculaire moyenne en poids (Mw) comprise entre 35000 et 150000, (2) une répartition du poids moléculaire (Mw/Mn) inférieure ou égale à 3, et (3) un point de ramolissement compris entre 80 et 130°C ; et (C) une résine thermoplastique. La teneur en composant (A) est comprise entre 1 et 14% en masse pour 100% en masse au total des composants (A) à (C), et la teneur en composant (B) est comprise entre 0,5 et 2 fois la masse du composant (A).
PCT/JP2017/027785 2016-08-03 2017-07-31 Composition de résine conductrice WO2018025824A1 (fr)

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CN110698838A (zh) * 2019-10-30 2020-01-17 濮阳市盛通聚源新材料有限公司 一种基于聚碳酸酯的柔性导电薄膜及其制备方法
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