WO2018056215A1

WO2018056215A1 - Electroconductive resin composition

Info

Publication number: WO2018056215A1
Application number: PCT/JP2017/033483
Authority: WO
Inventors: 秀臣片野
Original assignee: 片野染革株式会社
Priority date: 2016-09-21
Filing date: 2017-09-15
Publication date: 2018-03-29
Also published as: JP2018048254A

Abstract

The purpose of the present invention is to provide an electroconductive resin composition usable in electroconductive fields such as the prevention of static build-up. The electroconductive resin composition is characterized by comprising (A) carbon nanotubes, (B) an olefin-based polymer having (1) a weight-average molecular weight (Mw) of 35,000-150,000, (2) a molecular-weight distribution (Mw/Mn) of 3 or less, and (3) a softening point of 80-130°C, (C) a thermoplastic resin comprising a polyamide resin ingredient, and (D) a copolymer of a maleic-anhydride-modified ethylene or propylene with a C_3-4 α-olefin, the content of component (A) being 1-14 mass% with respect to the total amount of (A) to (D), which is taken as 100 mass%, the content of component (B) being 0.5-2 times by mass the component (A) content, and the content of component (D) being 1-20 mass% with respect to the total amount of (A) to (D), which is taken as 100 mass%.

Description

Conductive resin composition

The present invention relates to a conductive resin composition containing carbon nanotubes and a polyamide resin.

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. Among these 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.

However, carbon nanotubes provided as a raw material, that is, a raw material are often provided in a fluffy aggregate. Therefore, in order to conduct electricity in the resin using the carbon nanotubes, it is required that the aggregate is dispersed and is appropriately dispersed in the resin.

Conventionally, 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. Here, regarding the conductive resin composition using carbon nanotubes, dispersion control of the carbon nanotubes in the resin is a major issue.

The present inventor has developed a conductive resin having a volume resistivity in the thickness direction of 100 Ω · cm or less, comprising a carbon nanotube, an olefin polymer satisfying the following (1) to (3), and a thermoplastic resin: A 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 1).

Also, it has been reported that a predetermined compatibilizing agent is effective for mixing a polyamide resin and a polyolefin resin (Patent Document 2). In the examples, maleic anhydride-modified ethylene-1-butene copolymer, maleic anhydride-modified ethylene-octene copolymer, and the like are used. Polyamide resin is polyamide 11, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, and polyamide 9T / 2M-8T.

Japanese Unexamined Patent Publication No. 2016-41806 JP 2013-147645 A

In the field of coloring plastics, in order to control the dispersion of the coloring pigment, 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. Furthermore, masterbatch technology that selects resins, plasticizers, and waxes that are compatible with both the pigment and the base resin, masters the pigment at a high concentration, and makes it easy to disperse the pigment into the base resin is also widely used. ing.

These pigment dispersion techniques can be used as a reference when dispersing carbon nanotubes, but cannot be used directly for dispersing carbon nanotubes.

In the technique described in Patent Document 1, the carbon nanotubes are mixed with a plasticizer and wax before mixing the carbon nanotubes with the base resin, thereby making the carbon nanotubes easy to disperse and improving the dispersibility of the carbon nanotubes. ing. However, in the case of carbon nanotubes, since the aspect ratio, specific surface area, and oil absorption are large, more plasticizers and waxes are required per unit mass than conventional materials such as pigments. Here, in order to improve dispersibility, it is well known that when these plasticizers and waxes are added in a large amount, the performance of the base resin is adversely affected by bleedout of these components or deterioration of mechanical properties. .

Therefore, materials and methods for dispersing carbon nanotubes well with little influence on the base resin were expected.

In Patent Document 1, the present inventor uses an olefin polymer of the following (1) to (3) to reduce the adverse effect on the performance of the base resin, such as bleed out and mechanical properties. Yes. This olefin polymer 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, and (3) a softening point of 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.

Then, 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.

Carbon nanotubes melt-mixed with this olefin polymer and thermoplastic resin become final products through various processes such as granulation, blending, molding, etc. In these processes, remelting and cooling solidification are performed. Will be repeated. During this time, it is an important issue to prevent the carbon nanotubes from aggregating and lowering the conductivity. In particular, when a crystalline resin is included in the thermoplastic resin, it is considered that carbon nanotubes tend to be unevenly distributed in the amorphous portion of the thermoplastic resin and the olefin polymer during the cooling and solidification process. In the process of commercialization, in order to obtain stable conductivity, a device for preventing re-aggregation of carbon nanotubes is very important. Until the final product is made, the problem is to make the carbon nanotubes in a dispersion suitable for electrical conductivity, and there is a need for means that can always obtain high electrical conductivity with a low concentration of carbon nanotubes.

Moreover, the thermoplastic resin composition of Patent Document 2 does not have electrical conductivity.

As a result of studying to solve the above problems, the present inventor, when the thermoplastic resin contains a carbon nanotube and a polyamide resin, blending a compatibilizer (component (D) of the present invention) described later. Then, it discovered that the said subject could be solved.

That is, the present invention provides the following [1] to [3].
[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. An olefin polymer,
(C) a thermoplastic resin containing a polyamide resin, and (D) a copolymer of maleic anhydride-modified ethylene or propylene and an α-olefin having 3 to 4 carbon atoms,
The content of the component (A) is 1 to 14% by mass with respect to 100% by mass in total of (A) to (D),
The content of the component (B) is 0.5 to 2 times the content of the component (A), and the content of the component (D) is 100% by mass in total of (A) to (D). On the other hand, a conductive resin composition characterized by being 1 to 20% by mass.
[2] The conductive resin composition according to [1], wherein the component (D) is a maleic anhydride-modified ethylene / 1-butene copolymer.
[3] A molded article using a cured product of the conductive resin composition according to [1] or [2].

The conductive resin composition of the present invention [1] is compared with a conventional conductive resin composition composed of carbon black, graphite, carbon nanotubes not containing a specific compatibilizer, the olefin polymer, and a polyamide resin. Thus, even when a small amount of carbon nanotubes are added, good conductivity is easily obtained, so that the moldability of resin using the conductive resin composition and mechanical properties (for example, flexural modulus, Charpy impact strength) are excellent. Has a remarkable effect.

Hereinafter, the present invention will be described in detail.

[Conductive resin composition]
The conductive resin composition of the present invention comprises (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,
(C) a thermoplastic resin containing a polyamide resin component, and (D) a copolymer of maleic anhydride-modified ethylene or propylene and an α-olefin having 3 to 4 carbon atoms,
The content of the component (A) is 1 to 14% by mass with respect to 100% by mass in total of (A) to (D),
The content of the component (B) is 0.5 to 2 times the content of the component (A), and the content of the component (D) is 100% by mass in total of (A) to (D). On the other hand, the content is 1 to 20% by mass.

[(A) Carbon nanotube]
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.

As the carbon nanotube of component (A), 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 μm 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 μm or more, the conductivity can be increased, and if it is 50 μm or less, an increase in viscosity during kneading can be suppressed and kneading and molding can be facilitated. . From the above viewpoint, 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 μm, still more preferably 0.6 to 15 μm. In addition, 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.

In addition, as 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.

[(B) Olefin polymer]
The (B) component olefin polymer used in the present invention satisfies the following (1) to (3).
(1) Weight average molecular weight (Mw) of 35,000 to 150,000
(2) Molecular weight distribution (Mw / Mn) is 3 or less (3) Softening point is 80-130 ° C

As the olefin polymer as the component (B), an olefin polymer obtained by polymerizing at least one monomer selected from ethylene and an α-olefin having 3 to 28 carbon atoms is preferable.

Examples of the α-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. Of these, α-olefins having 3 to 24 carbon atoms are preferable, α-olefins having 3 to 12 carbon atoms are more preferable, α-olefins having 3 to 6 carbon atoms are more preferable, and 3 to 4 carbon atoms are particularly preferable. An α-olefin, most preferably propylene.

As the 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. In the present specification, the term “olefin polymer” includes both olefin homopolymers and olefin copolymers.

As the olefin polymer of component (B), an ethylene polymer in which 50 mol% or more of the monomer constituting the polymer is an ethylene monomer, or a propylene monomer in which 50 mol% or more of the monomer constituting the polymer is a propylene monomer 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.

Examples of the propylene polymer (1) include propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene It is preferably a propylene-based polymer selected from a butene random copolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin graft copolymer, etc., and a conductive resin composition is used. From the viewpoint of the mechanical strength of the molded product, a propylene homopolymer is particularly preferable.

In the propylene polymer (1), the content of the structural unit of the α-olefin having 3 carbon atoms (that is, propylene monomer) 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.

Further, as the olefin polymer of the component (B), a propylene polymer (2) satisfying at least one of the following (i) and (ii) can also be used.
(I) A structural unit of ethylene is contained in an amount of more than 0 mol% and 25 mol% or less.
(Ii) The structural unit of 1-butene is contained in an amount of more than 0 mol% and not more than 30 mol%.

In the case where 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. In the case of a copolymer containing an α-olefin having 4 or more carbon atoms (ie, 1-butene monomer), 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 the physical properties of the molded product due to heat resistance and bleed out, and are limited in use. Arise. In addition, with a resin having a weight average molecular weight (Mw) exceeding 150,000, it is difficult to disperse the component (A). From the above viewpoint, the weight average molecular weight (Mw) is preferably 40,000 to 140,000, more preferably 42,000 to 130,000.

Also, by using an olefin polymer having a molecular weight distribution (Mw / Mn) of 3 or less, it is possible to eliminate the adverse effects of low molecular weight components and high molecular weight components that affect product properties. From the above viewpoint, the molecular weight distribution (Mw / Mn) is preferably 2.8 or less, more preferably 2.5 or less.

Furthermore, by using an olefin polymer having a softening point of 80 to 130 ° C., the dispersibility of the component (A) can be improved and the processing temperature can be lowered. From the above viewpoint, the softening point is preferably 90 to 125 ° C, more preferably 93 to 120 ° C.

As the component (B), an olefin polymer synthesized with a metallocene catalyst is suitable.

In the present invention, 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). In addition, 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).

<< GPC measuring device >>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
〔Measurement condition〕
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
In the present invention, the softening point is determined in accordance with the ball ring method ISO4625.

[(C) Thermoplastic resin containing polyamide resin]
Examples of the thermoplastic resin containing the polyamide resin of component (C) used in the present invention include polyamide resins containing amino groups, such as polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6T, Polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, and polyamide MXD6.

The component (C) is also effective as a block copolymer containing two or more blended thermoplastic resins of the above polyamide resin and a polyamide resin component. Examples of the block copolymer containing a polyamide resin component include polyamide elastomers which are block copolymers using polyether diol and polyester diol. Specific examples include polytetramethylene ether glycol and polyoxypropylene bricol.

Furthermore, the component (C) contains a polyamide resin component that uses a copolymer of maleic anhydride-modified ethylene or propylene, which is the component (D), and an α-olefin having 3 to 4 carbon atoms as a compatibilizing agent. It is also effective against alloys that Examples of the resin that forms an alloy with the polyamide resin include polyethylene resin, polypropylene resin, polyolefin elastomer resin, ABS resin, polycarbonate resin, polyphenylene ether resin, and polyarylate resin.

[(D) Copolymer of Maleic Anhydride-Modified Ethylene or Propylene and C3-C4 α-Olefin]
Component (D) is a compatibilizing agent and is a copolymer of ethylene or propylene to which a reactive group capable of reacting with a polyamide resin is added and an α-olefin having 3 to 4 carbon atoms. Specific examples include a copolymer of ethylene or propylene modified with maleic anhydride and an α-olefin having 3 to 4 carbon atoms. The maleic anhydride moiety of this copolymer is bonded to the amino group component of the polyamide resin, and the copolymer moiety of ethylene or propylene other than the maleic anhydride moiety and the α-olefin having 3 to 4 carbon atoms is an olefinic group. The present inventor has found that it is compatible with the polymer and contributes to the improvement of conductivity by the carbon nanotube. The clear mechanism for improving the conductivity has not been fully analyzed. However, a copolymer of maleic anhydride-modified ethylene or propylene and an α-olefin having 3 to 4 carbon atoms is added to the carbon nanotube. It is considered that the carbon nanotubes are prevented from being re-aggregated and appropriately dispersed, and the electrical connection between the carbon nanotubes is maintained well.

Therefore, the present invention is a polyamide resin containing an amino group component, such as polyamide 11, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, This is effective for improving the conductivity of polyamide 1012, polyamide 10T, and polyamide MXD6.

The present invention can also be applied to two or more blended compositions of the above polyamide resins and block copolymers containing polyamide resin components. Examples of the block copolymer containing a polyamide resin component include polyamide elastomers which are block copolymers using polyether diol and polyester diol. Specific examples include polytetramethylene ether glycol and polyoxypropylene bricol. The present invention is also effective when imparting conductivity to these using carbon nanotubes and olefinic polymers.

Furthermore, it can be applied to many resins that form alloys with polyamide resins by using a copolymer of ethylene or propylene modified with maleic anhydride and an α-olefin having 3 to 4 carbon atoms as a compatibilizing agent. Specific examples of resins that form alloys with polyamide resins include polyethylene resins, polypropylene resins, polyolefin elastomer resins, ABS resins, polycarbonate resins, polyphenylene ether resins, and polyarylate resins. The present invention is also effective when imparting conductivity using a polymer.

Many copolymers of ethylene or propylene modified with maleic anhydride and α-olefins having 3 to 4 carbon atoms are commercially available and can be used widely.

On the other hand, α-olefins having 5 or more carbon atoms used for copolymerization are also considered effective. For example, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, Examples thereof include 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene and the like.

Among these copolymers of ethylene anhydride or propylene modified with maleic anhydride and an α-olefin having 3 to 4 carbon atoms, particularly maleic anhydride modified ethylene / 1-butene copolymer has a low softening temperature. It is easy to use and preferable.

Hereinafter, the case where the component (D) is a maleic anhydride-modified ethylene / 1-butene copolymer will be described.

Among copolymers of ethylene anhydride or propylene modified with maleic anhydride and an α-olefin having 3 to 4 carbon atoms, particularly ethylene / 1-butene copolymer modified with maleic anhydride has a low softening temperature. The present inventor believes that it is suitable for controlling the compatibility of the component (B) with the olefin polymer and the dispersibility of the carbon nanotubes. In addition, as a secondary effect, the maleic anhydride-modified ethylene / 1-butene copolymer improves the low temperature impact resistance of the conductive resin composition.

The content ratio of the four components (A) to (D) of the conductive resin composition affects the conductivity and mechanical properties of the molded body using the conductive resin composition. The content of the four components is adjusted.

The content of the component (A) is 1 to 14% by weight, preferably 2 to 10% by weight, more preferably 2 to 8% by weight, based on 100% by weight of the total of the components (A) to (D). It is. When the content of the component (A) is less than 1% by mass, conductivity may not be exhibited. On the other hand, if the content of the component (A) exceeds 14% by mass, the electrical conductivity increases, but the content of the component (C) decreases, so the mechanical properties of the molded body using the conductive resin composition 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 the electroconductivity of the molded object using the conductive resin composition. On the other hand, when the content of the component (B) exceeds twice, the molded body using the conductive resin composition tends to be soft.

The content of the component (D) is 1 to 20% by mass, preferably 2 to 17% by mass, more preferably 2 to 15% by mass, with respect to 100% by mass of the total of the components (A) to (D). It is. If the content of the component (D) is less than 1% by mass, the effect of adding high conductivity to a molded body using the conductive resin composition may be insufficient. On the other hand, when the content of the component (D) exceeds 20% by mass, the conductivity of the molded body using the conductive resin composition is lowered. Although the reason why the conductivity of the molded article using the conductive resin composition is lowered when the content of the component (D) exceeds 20% by mass has not been fully clarified, the component (D) While it contributes to the dispersion of the carbon nanotubes, it is thought that if the amount is too large, it interferes with the electrical connection between the carbon nanotubes.

The content of the component (C) is the balance obtained by subtracting the contents of the components (A), (B), and (D) from the total 100% by mass of the components (A) to (D). Therefore, when the content of the component (A), the component (B), and the component (D) increases, the content of the component (C) relatively decreases. In order to balance electrical conductivity and mechanical properties, it is necessary to ensure the content of the component (C). For that purpose, the content of the component (A) is as small as possible, and the conductive resin composition It is important to develop conductivity in a molded body using a product.

[Other ingredients]
The conductive resin composition of the present invention is a non-conductive inorganic filler generally contained in this type of composition, for example, calcium carbonate, as long as the effects of the present invention are not impaired in addition to the above components. Additives such as precipitated barium sulfate, talc, diatomaceous earth, mica, glass, alumina, magnesium carbonate, calcium sulfate; lubricant; antistatic agent; ultraviolet absorber; pigment; .

[Method for producing conductive resin composition]
Next, an example of the manufacturing method of the above-mentioned conductive resin composition will be described.

First, an example of the method for producing the conductive resin composition of the present invention is to stir the components (A) and (B) at a temperature of 90 ° C. or higher and a stirring speed of 300 rpm or higher to obtain a mixture. It is a method of adding a component (C) and a component (D) to obtain a resin composition.

The production of the conductive resin composition of the present invention will be described in detail. The component (A) and the component (B) are charged into a mixer and stirred and mixed at a temperature higher than the temperature at which the component (B) is softened, that is, 90 ° C. or higher and a stirring speed of 300 rpm or higher. Is loosened, and the component (B) adheres to the surface of the component (A). Thus, (B) component adheres to the surface of (A) component, and at the time of melt-kneading (C) component and (D) component, (A) component becomes (C) component and (D) It becomes a factor that easily mixes with the component, and enables the (A) component to be highly dispersed into the (C) component and the (D) component.

The stirring temperature is preferably 100 to 180 ° C., more preferably 120 to 160 ° C., and 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. As 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.

As a mixing method, 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.

By the above mixing, a powdery mixture in which the surface of the component (A) is coated with the component (B) can be obtained.

Next, the obtained mixture (powder mixture) of the component (A) and the component (B) is added to the component (C) and the component (D) and mixed.

The mixture of the component (A) and the component (B) (powder mixture), the mixture of the component (C) and the component (D) is melt-kneaded with a single-screw or twin-screw extruder and extruded into a strand shape into pellets. A conductive resin composition can be obtained by granulating. The heating temperature in melt kneading is preferably 150 to 600 ° C., more preferably 200 to 500 ° C.

In addition, the mixture (powder mixture), the component (C) and a part of the component (D) are melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, granulated into pellets, and the next step A so-called master batch method may be used in which the remaining components (C) and (D) are mixed, melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, and granulated into pellets.

According to the above-described production method, the carbon nanotubes of component (A) can be highly dispersed in the resin, so that the conductive material can be molded with a small amount of addition and has excellent mechanical properties. Resin composition. The above-described manufacturing method is simple and excellent in cost reduction.

The melt flow rate (MFR) of the conductive resin composition obtained by the above production method is preferably 0.1 to 100 g / 10 min, more preferably 0.3 to 50 g / 10 min.

The volume resistivity of the molded body using the cured product of the conductive resin composition is preferably 1 × 10 ⁷ to 1 × 10 ¹ Ω · cm, more preferably 1 × 10 ⁶ to 2 × 10 ¹ Ω · cm. It is.

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.

In addition, the measurement of each physical property value can be specifically measured by the method described in the examples.

[Molded body using conductive resin composition]
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.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. In addition, the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

In all the examples and comparative examples, the component (A) and the component (B) were passed through the preparation of the mixture (powder mixture), and then the mixture (powder mixture) was mixed with the component (C) and (D). The components were added, and this was carried out by the production method for the melt kneading and granulating step in the next step.

[Bending test and Charpy impact test sample preparation]
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 350 ° C.

[Evaluation of physical properties]
(1) Measurement of volume resistivity In sample preparation by injection molding, a plate having a length of 13 mm × width of 180 mm and a thickness of about 3 mm was prepared by an injection molding machine. Cut out a volume resistivity measurement piece from the center of the plate, measuring 13 mm in length × 30 mm in width and about 3 mm in thickness, and using a resistivity meter (Loresta GPMCCP-T610, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) Was measured. The volume resistivity is preferably 1 × 10 ⁷ Ω · cm or less.

(2) Melt flow rate (MFR)
According to JIS K7210, it was measured by a melt indexer (manufactured by Toyo Seiki Seisakusho, P-01 type). The measurement temperature and load are shown in Tables 1 and 2. The MFR is preferably 0.1 g / 10 min or more.

(3) Bending test Based on JIS K7203, the bending elastic modulus was measured with a precision universal testing machine (manufactured by Shimadzu Corporation, AGS-500A type). The bending elastic modulus is preferably 200 MPa or more.

(4) Charpy impact strength Based on JIS K7111, it was measured with a universal pendulum impact tester (CEAST, 6545/000 type). The Charpy impact strength is preferably 0.5 KJ / m ² or more.

Details of each component used in the examples and comparative examples are as follows.
[(A) component: carbon nanotube]
(A-1): “NC7000” manufactured by Nanocyl (average diameter 9.5 nm, average length 1.5 μm)
(A-2): “C-100” manufactured by Arkema (average diameter 13 nm, average length 4 μm)
[(B) component: olefin polymer]
(B-1): “Ilmodu S400” manufactured by Idemitsu Kosan Co., Ltd. (metallocene catalyst low stereoregular polyolefin, Mw = 45,000, (Mw / Mn) = 2, softening point: 93 ° C.)
(B-2): “Ilmodu S901” manufactured by Idemitsu Kosan Co., Ltd. (metallocene catalyst low stereoregular polyolefin, Mw = 130,000, (Mw / Mn) = 2, softening point: 120 ° C.)
[Component (C): Thermoplastic resin containing polyamide resin component]
(C-1): “Nylon resin injection 1013B” (PA6), manufactured by Ube Industries, Ltd.
(C-2): “Rilsan BMF O” (PA11), manufactured by Arkema
(C-3): “MX Nylon S6007” (PA MXD6) manufactured by Mitsubishi Gas Chemical Company, Inc.
(C-4): “Pebax 4533SP01” manufactured by Arkema (copolymer of PA elastomer PA12 and polytetramethylene ether glycol)
[Component (D): Copolymer of ethylene or propylene modified with maleic anhydride and an α-olefin having 3 to 4 carbon atoms]
(D-1): “Tuffmer MH5040” manufactured by Mitsui Chemicals, Inc. (maleic anhydride modified ethylene / 1-butene copolymer, MFR (230 ° C.): 1.1 g / 10 min)
(D-2): “Tafmer MH7020” (maleic anhydride modified ethylene / 1-butene copolymer, MFR (230 ° C.): 1.5 g / 10 min), manufactured by Mitsui Chemicals, Inc.
(D-3): “Tafmer DF610” (ethylene / 1-butene copolymer, MFR (230 ° C.): 2.2 g / 10 min) manufactured by Mitsui Chemicals, Inc.

[Examples 1 to 5 and Comparative Examples 1 to 5]
The components (A) and (B) shown in Tables 1 and 2 were charged in an FM mixer (FM10C / I, capacity: 9 dm ³ ) manufactured by Nippon Coke Industries Co., Ltd. The mixture was stirred and mixed under the conditions of a stirring time of 60 minutes and a rotation speed of 1000 rpm to obtain a powdery mixture. According to JIS K5101, the bulk density of the carbon nanotube “NC7000” of (A-1) and the powdered mixture of the obtained components (A) and (B) was measured. Was 0.07 g / cm ³ , and the powder mixture was 0.40 g / cm ³ .

Thereafter, the obtained powder mixture, the components (C) and (D) having the contents shown in Tables 1 and 2 were dry blended, and then a twin-screw extruder (manufactured by 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 Tables 1 and 2. Further, 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 conductive resin compositions. In Tables 1 and 2, a blank represents no inclusion.

From Tables 1 and 2, we found the following. In Example 1 in which the content of the component (A) and the component (B) are the same, and the content of the component (D) is 6.0% by mass and Comparative Example 1 in which the content is 0.5% by mass, Example 1 The volume resistivity was smaller, the flexural modulus was larger, and the Charpy impact strength was larger. Therefore, Example 1 was superior as a conductive resin composition. It is considered that by adding an appropriate amount of the component (D), the dispersion of the carbon nanotubes is improved and the conductivity is improved. Further, it is considered that the improvement of the flexural modulus and the Charpy impact strength was caused by the improved dispersion of the carbon nanotubes.

In Example 1 in which the content of the component (A) and the component (B) are the same, and the content of the component (D) is 6.0% by mass, and Comparative Example 2 in which the content is 25.0% by mass, Example 1 The volume resistivity was smaller and the flexural modulus was larger. Regarding Charpy impact strength, Comparative Example 2 was larger. With the increase in the content of the component (D), Comparative Example 2 shifted to a soft characteristic, but the volume resistivity significantly increased. This is considered to be because the content of the component (D) is too large, and the formation of the conductive circuit by the carbon nanotubes has been hindered. Even if there was too little content of (D) component, the favorable conductive resin composition was not obtained.

Comparing Comparative Example 3 and Example 1 in which the content of the carbon nanotube as the component (A) is increased to 18.0% by mass, Comparative Example 3 has smaller volume resistivity and better electrical conductivity. As shown, the MFR was small, the flexural modulus was large, and the Charpy impact strength was remarkably low. In Comparative Example 3, it was very difficult to flow at the time of melting (that is, the moldability was poor), and the molded body was hard and brittle, so that it was not suitable for practical use as a molded body. Comparative Example 3 did not exhibit the effects of the present invention aimed at a resin having both good conductivity with a small amount of carbon nanotubes and excellent moldability and mechanical properties.

When Comparative Example 4 in which the content of the carbon nanotube as the component (A) is reduced to 0.5 mass% is compared with Example 1, the volume resistivity of Comparative Example 4 exceeds 1 × 10 ⁷ Ω · cm. The conductivity was poor.

Comparative Example 5 and Example 1 using an ethylene / 1-butene copolymer not modified with maleic anhydride instead of the maleic anhydride modified ethylene / 1-butene copolymer as component (D) In comparison, the volume resistivity of Comparative Example 5 is remarkably high at 3 × 10 ⁴ Ω · cm, and the MFR, flexural modulus, and Charpy impact strength are almost the same, but as a molded article of the conductive resin composition It was not suitable for practical use.

In Example 2, compared with Example 1, the component (B) is changed from (B-1) to (B-2), the component (D) is changed from (D-1) to (D-2). Changed, but with good results.

In Example 3, compared with Example 1, the component (C) was changed from (C-1) to (C-2), but the result was good.

In Example 4, compared with Example 1, the component (A) is changed from (A-1) to (A-2), the component (C) is changed from (C-1) to (C-3). Changed, but with good results.

In Example 5, compared with Example 1, the component (A) is changed from (A-1) to (A-2), the component (C) is changed from (C-1) to (C-4). Changed, but with good results. In Example 5, the volume resistivity was significantly reduced to 9 × 10 ⁻¹ Ω · cm by increasing the content of the carbon nanotube as the component (A) to 10.0% by mass. (C-4) is a polyamide elastomer of a thermoplastic resin containing a polyamide resin component.

From a bird's-eye view of Examples and Comparative Examples, the component (D) is a maleic anhydride-modified ethylene or propylene copolymer with a C 3-4 α-olefin, specifically maleic anhydride. Good results were obtained for Examples 1 to 5 in which the acid-modified ethylene / 1-butene copolymer was added within the scope of the present invention. On the other hand, Comparative Examples 1 to 5 outside the scope of the present invention were inferior to Examples 1 to 5, indicating that the present invention has a remarkable effect.

The molded body made of the conductive resin composition of the present invention is easy to obtain good conductivity even when a small amount of carbon nanotubes are added, compared to carbon black and graphite conventionally used as a conductivity imparting agent. Therefore, the resin using the conductive resin composition is excellent in moldability and mechanical properties, and is suitable for injection molded products, extrusion molded products, films, and sheets that require antistatic properties.

Claims

(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,
(C) a thermoplastic resin containing a polyamide resin, and (D) a copolymer of maleic anhydride-modified ethylene or propylene and an α-olefin having 3 to 4 carbon atoms,
The content of the component (A) is 1 to 14% by mass with respect to 100% by mass in total of (A) to (D),
The content of the component (B) is 0.5 to 2 times the content of the component (A), and the content of the component (D) is 100% by mass in total of (A) to (D). On the other hand, a conductive resin composition characterized by being 1 to 20% by mass.
The conductive resin composition according to claim 1, wherein component (D) is a maleic anhydride-modified ethylene / 1-butene copolymer.
A molded body using a cured product of the conductive resin composition according to claim 1 or 2.