JP2021147606A - Resin composition and molding of the same - Google Patents

Abstract

SOLUTION: There is provided a resin composition (X) that contains 80.0-99.9 pts.mass of a thermoplastic resin (A) and 0.1-20.0 pts.mass of a carbon-based filler (B) (total of thermoplastic resin (A) and carbon-based filler (B) is 100 pts.mass), and satisfies the following requirements (a) to (c): requirement (a); a temperature in which a loss tangent tanδ obtained by dynamic viscoelasticity at a frequency of 10 rad/s (1.6 Hz) in a temperature range of -40 to 150°C becomes a peak value of 0°C or higher and 60°C or lower, requirement (b); a peak value of a loss tangent tanδ obtained by dynamic viscoelasticity at a frequency of 10 rad/s (1.6 Hz) in a temperature range of -40 to 150°C of 0.5 or more and 5.0 or less, and requirement (c); surface resistivity of 10^14 Ω or less.EFFECT: A resin composition has a high tanδ peak value at room temperature, has excellent electric characteristics and mechanical properties, and enables formation of a molding which has a high tanδ peak value at room temperature irrespective of a molding method, has excellent electric characteristics and is excellent in mechanical properties.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and a molded product, and more particularly to a resin composition containing a carbon-based filler and a molded product molded using the same.

More specifically, the present invention is a combination of 4-methyl-1-pentene and α-olefin, which are excellent in stress absorption, stress relaxation, electrical properties, toughness, and mechanical properties, and whose shrinkage rate after molding is suppressed. The present invention relates to a composition containing a polymer and a carbon-based filler, and a molded product formed by using the composition.

Olefin-based polymers are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion-molded products, injection-molded products, hollow-molded products, films, sheets, fibers, etc. It is used for various purposes such as miscellaneous goods, kitchen utensils, packaging films, non-woven fabrics, home appliances, mechanical parts, electrical parts, and automobile parts.

Patent Document 1 and Patent Document 2 disclose a material having a high tan δ peak at room temperature, which is made of a 4-methyl-1-pentene copolymer, and uses this material as a vibration damping and vibration damping member. It is also disclosed that it adapts to. The vibration damping property required for the damping material can be evaluated by, for example, the loss tangent tan δ, which is the ratio (G ″ / G ′) of the storage elastic modulus (G ′) and the loss elastic modulus (G ″). Therefore, the higher the tan δ in the temperature environment in which the damping material is used, the stronger the viscosity is exhibited, so that the stress due to vibration is easily absorbed and the higher damping property is exhibited. Since tan δ changes depending on the temperature, the maximum value of tan δ of the damping material (hereinafter, also referred to as “tan δ peak value”) and the temperature at which the value of tan δ is maximum (hereinafter, also simply referred to as “tan δ peak temperature”). Technology has been developed to adjust) to a specific range.

Japanese Unexamined Patent Publication No. 2012-82388 JP-A-2017-132920

Although the materials described in the above-mentioned Patent Documents 1 and 2 have a high tan δ peak value at room temperature, further improvement has been required from the viewpoint of electrical characteristics.
By imparting conductivity, static electricity can be suppressed when used in the above-mentioned various applications, and it can be applied to elastic conductive wiring, electrodes, sensors, and the like.

Therefore, an object of the present invention is to provide a resin composition and a molded product having a high tan δ peak value at room temperature and further having excellent electrical characteristics and mechanical characteristics.

As a result of diligent research in view of the above circumstances, the present inventors have completed the present invention.
That is, the present invention relates to the following [1] to [11].

[1]
A thermoplastic resin which is an olefin-based copolymer containing a structural unit (i) derived from an α-olefin having 6 to 20 carbon atoms and a structural unit (ii) derived from an α-olefin having 2 to 5 carbon atoms. (A) 80.0 to 99.9 parts by mass and carbon-based filler (B) 0.1 to 20.0 parts by mass (the total of the thermoplastic resin (A) and the carbon-based filler (B) is 100 parts by mass. The resin composition (X), which comprises the above and satisfies the following requirements (a) to (c):
Requirement (a); The temperature at which the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C is 0 ° C or higher. It is 60 ° C. or lower.
Requirement (b); The peak value of the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C. is 0.5 or more. It is 0 or less.
Requirement (c); The surface resistivity is 10 ^ 14Ω or less.
[2]
80.0 to 99.9 parts by mass of the thermoplastic resin (A) and 0.1 to 20.0 parts by mass of the carbon-based filler (B) (the total of the thermoplastic resin (A) and the carbon-based filler (B) is 100. The resin composition (X), which comprises (part by mass) and satisfies the following requirements (a) to (c):
Requirement (a); The temperature at which the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C is 0 ° C or higher. It is 60 ° C. or lower.
Requirement (b); The peak value of the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C. is 0.5 or more. It is 0 or less.
Requirement (c); The surface resistivity is 10 ^ 14Ω or less.
[3]
The thermoplastic resin (A) is a 4-methyl-1-pentene / α-olefin copolymer (A-1) in which the α-olefin having 6 or more and 20 or less carbon atoms is 4-methyl-1-pentene. The resin composition (X) according to the above [1].
[4]
The resin composition (X) according to the above [3], wherein the 4-methyl-1-pentene / α-olefin copolymer (A-1) satisfies the following requirements (d) to (g). ):
Requirement (d); The copolymer (A-1) is a structural unit (i) derived from 4-methyl-1-pentene and a structural unit (ii) derived from an α-olefin having 2 or more and 5 or less carbon atoms. Assuming that the total of the above is 100 mol%, the constituent unit (i) 55 to 90 mol% and the constituent unit (ii) 10 to 45 mol% are included.
Requirement (e); The copolymer (A-1) has a melting point (Tm) of 160 ° C. or less as measured by a differential scanning calorimeter (DSC) or a melting point measured by a differential scanning calorimeter (DSC). Not done.
Requirement (f); The copolymer (A-1) has a loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150 ° C. The peak temperature is 15 ° C. or higher and 45 ° C. or lower.
Requirement (g); The copolymer (A-1) has a loss tangent tan δ obtained by performing a dynamic viscoelastic measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150 ° C. The peak value is 0.6 or more and 5.0 or less.
[5]
The resin composition (X) according to any one of the above [1] to [4], wherein the carbon-based filler (B) is a carbon nanotube.
[6]
A molded product containing the resin composition (X) according to any one of the above [1] to [5].
[7]
A sheet containing the resin composition (X) according to any one of [1] to [5].
[8]
A toy containing the resin composition (X) according to any one of [1] to [5].
[9]
Daily sundries containing the resin composition (X) according to any one of [1] to [5].
[10]
An automobile material containing the resin composition (X) according to any one of the above [1] to [5].
[11]
An electronic component containing the resin composition (X) according to any one of [1] to [5].

The resin composition of the present invention has a high tan δ peak value at room temperature, further excellent electrical characteristics and mechanical characteristics, has a high tan δ peak value at room temperature regardless of the molding method, and has excellent electricity. It is possible to form a molded body having characteristics and further having excellent mechanical properties.

Hereinafter, the resin composition and the molded product of the present invention will be described.
[Resin composition (X)]
The resin composition (X) of the present invention contains a thermoplastic resin (A) and a carbon-based filler (B).
The resin composition (X) of the present invention may contain only the thermoplastic resin (A) and the carbon-based filler (B), or as will be described later, the thermoplastic resin (A) and the carbon-based filler (B). In addition to the filler (B), other components that are neither the thermoplastic resin (A) nor the carbon-based filler (B) may be further contained. Further, the resin composition (X) of the present invention satisfies the following requirements (a) to (c).

Requirement (a);
The resin composition (X) of the present invention has a temperature in which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s reaches a peak value in the temperature range of -40 to 150 ° C. (hereinafter, “tan δ”). The peak temperature) is 0 ° C. or higher and 60 ° C. or lower.
The tan δ peak temperature is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 45 ° C. or lower, and particularly preferably 25 ° C. or higher and 43 ° C. or lower.

Requirement (b);
The resin composition (X) of the present invention has a peak value of tangent tan δ (hereinafter referred to as tangent tan δ) obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150 ° C. (Also referred to as “tan δ peak value”) is 0.5 or more and 5.0 or less.
The tan δ peak value is preferably 0.6 or more and 4.5 or less from the viewpoint of flexibility, and more preferably 0.7 or more and 3.5 or less. tan δ is the ratio of the storage elastic modulus (G') to the loss elastic modulus (G ″) using the storage elastic modulus (G ′) and the loss elastic modulus (G ″) obtained when measuring the dynamic viscoelasticity. It can be calculated as G "/ G': loss tangent).

Here, in the present invention, the temperature at which tan δ reaches the peak value (maximum value) in the range of -40 to 150 ° C. is defined as the temperature at which tan δ reaches the peak value, and the value of tan δ at that time is the tan δ peak. Let it be a value. The peak is considered to be due to the glass transition temperature of the thermoplastic resin composition.

Requirement (c);
The resin composition (X) of the present invention has a surface resistivity of 10 ^ 14Ω or less.

Hereinafter, the thermoplastic resin (A) and the carbon-based filler (B) constituting the resin composition (X) of the present invention will be described.
<Thermoplastic resin (A)>
The resin composition (X) of the present invention contains a thermoplastic resin (A).
The content ratio of the thermoplastic resin (A) in the resin composition (X) is 80.0 to 99.9 parts by mass, where the total of the thermoplastic resin (A) and the carbon-based filler (B) is 100 parts by mass. , Preferably 85.0 parts by mass or more, more preferably 90.0 parts by mass or more, preferably 99.5 parts by mass or less, more preferably 99.2 parts by mass or less, still more preferably 99.0 parts by mass or less. Is.

Here, the thermoplastic resin (A) used in the present invention is as long as the problem of the present invention can be solved, and in particular, as long as the resin composition (X) having the peak temperature and peak value of tan δ can be provided. It is not particularly limited. However, in a typical embodiment of the present invention, the thermoplastic resin (A) is derived from a structural unit (i) derived from an α-olefin having 6 or more and 20 or less carbon atoms and an α-olefin having 2 or more and 5 or less carbon atoms. An olefin-based copolymer containing the structural unit (ii) to be obtained is preferable from the viewpoint of impact resistance, and among the olefin-based copolymers, the α-olefin having 6 or more and 20 or less carbon atoms is 4-methyl-1-. A 4-methyl-1-pentene / α-olefin copolymer (A-1), which is a penten, is particularly preferable.
Hereinafter, the 4-methyl-1-pentene / α-olefin copolymer (A-1) will be described.

<< 4-Methyl-1-pentene / α-olefin copolymer (A-1) >>
The 4-methyl-1-pentene / α-olefin copolymer (A-1) (hereinafter, also simply referred to as “copolymer (A-1)”) meets the following requirements (d) to (g). It is preferable to satisfy all. The 4-methyl-1-pentene / α-olefin copolymer (A-1) can be used alone or in combination of two or more. Further, as a more preferable aspect of the present invention, the following requirements (d) to (k) will be described in detail below.

Requirement (d);
The 4-methyl-1-pentene / α-olefin copolymer (A-1) is derived from the structural unit (i) derived from 4-methyl-1-pentene and the α-olefin having 2 or more and 5 or less carbon atoms. When the total of the constituent unit (ii) to be obtained is 100 mol%, the constituent unit (i) is preferably 55 mol% to 90 mol% and the constituent unit (ii) is 10 mol% to 45 mol%.
The content (mol%) of each structural unit (4-methyl-1-pentene and α-olefin) in the 4-methyl-1-pentene copolymer (A) is ^{measured by 13} C-NMR.

Here, in the present invention, the term "structural unit derived from α-olefin" refers to a structural unit corresponding to α-olefin, that is, _{a structural unit represented by -CH 2-} CHR- (R is an alkyl group). Means. The same interpretation applies to "a structural unit derived from 4-methyl-1-pentene", which is a structural unit corresponding to 4-methyl-1-pentene (that is, -CH _2- CH (-CH ₂ CH (CH ₃ )). ₂ )-(R is a structural unit represented by an alkyl group)).

The lower limit of the proportion of the structural unit (i) constituting the 4-methyl-1-pentene / α-olefin copolymer (A-1) is preferably 55 mol%, but may be 60 mol%. More preferably, it is particularly preferably 68 mol%. On the other hand, the upper limit of the ratio of the constituent unit (i) is preferably 90 mol%, more preferably 86 mol%, and particularly preferably 84 mol%. When the ratio of the structural unit (i) constituting the 4-methyl-1-pentene / α-olefin copolymer (A-1) is equal to or higher than the above lower limit, both 4-methyl-1-pentene / α-olefin are present. Since the temperature at which the tan δ of the polymer (A-1) reaches its peak value is near room temperature, the temperature at which the tan δ of the resin composition reaches its peak value can be easily adjusted within the above-mentioned range.

As a matter of course, at this time, the upper limit of the ratio of the constituent unit (ii) is preferably 45 mol%, more preferably 40 mol%, and particularly preferably 32 mol%. On the other hand, the lower limit of the ratio of the constituent unit (ii) is preferably 10 mol%, more preferably 14 mol%, and particularly preferably 16 mol%.

Here, in a typical embodiment of the present invention, as an example of an α-olefin having 2 or more and 5 or less carbon atoms for deriving the structural unit (ii), a linear chain such as ethylene, propylene, 1-butene, and 1-pentene is used. Α-olefins and branched α-olefins such as 3-methyl-1-butene can be mentioned. Among these, ethylene, propylene, 1-butene and 1-pentene are preferable, and ethylene and propylene are particularly preferable. The structural unit (ii) may be derived from one of these compounds, or may be derived from two or more compounds.

However, the amount of 4-methyl-1-pentene / α-olefin copolymer (A-1) is small enough not to impair the object of the present invention (for example, the sum of the structural unit (i) and the structural unit (ii)). 10 mol% or less, where 100 mol% is defined as), in addition to the constituent unit (i) and the constituent unit (ii), 4-methyl-1-pentene and the constituent unit (ii) are used as the constituent unit (iii). It may further contain structural units derived from other monomers that are neither of the resulting α-olefins. As a preferable specific example of such another monomer, if the copolymer (A-1) is a 4-methyl-1-pentene-propylene copolymer, 5-vinyl-2-norbornene, 5 − Ethylidene-2-Norbornene and the like.

Requirement (e);
The 4-methyl-1-pentene / α-olefin copolymer (A-1) preferably has a melting point (Tm) of 160 ° C. or lower or a differential scanning calorimetry as measured by a differential scanning calorimeter (DSC). The melting point (Tm) is not measured by the meter (DSC). When the copolymer (A-1) satisfies such a requirement, the resin composition of the present invention can be easily kneaded with a carbon-based filler, and can improve vibration absorption and stress relaxation. It becomes.

Requirement (f);
The 4-methyl-1-pentene / α-olefin copolymer (A-1) was subjected to dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150 ° C. The obtained tan δ peak temperature is preferably 15 ° C. or higher and 45 ° C. or lower.
The tan δ peak temperature is more preferably 20 ° C. or higher and 40 ° C. or lower, and particularly preferably 25 ° C. or higher and 40 ° C. or lower. By setting the tan δ peak temperature in the above temperature range, the value of tan δ at room temperature can be further increased.

Requirement (g);
The 4-methyl-1-pentene / α-olefin copolymer (A-1) was subjected to dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150 ° C. The obtained tan δ peak value is preferably 0.6 or more and 5.0 or less.
The tan δ peak value is more preferably 1.0 or more and 5.0 or less, further preferably 1.5 or more and 5.0 or less, and particularly preferably 2.0 or more and 4.0 or less. By setting the tan δ peak value in the above range, the vibration absorption, the hardness of the material, and the followability can be changed according to the speed of tension and deformation.

In addition to the above requirements (d) to (g), the 4-methyl-1-pentene / α-olefin copolymer (A-1) has the following requirements (h), (i), (j) and ( It is further preferred to meet one or more requirements selected from k).

Requirement (h);
The ultimate viscosity [η] of the 4-methyl-1-pentene / α-olefin copolymer (A-1) measured at 135 ° C. in decalin is preferably 0.1 dL / g or more and 5.0 dL / g or less. be. The ultimate viscosity [η] is more preferably 0.5 dL / g or more and 4.0 dL / g or less, and further preferably 0.5 dL / g or more and 3.5 dL / g or less. The 4-methyl-1-pentene / α-olefin copolymer (A-1) having the above-mentioned ultimate viscosity [η] in the above-mentioned range can be easily formed into a sheet-shaped thermoplastic resin composition.

The extreme viscosity [η] of the 4-methyl-1-pentene / α-olefin copolymer (A-1) is within the above range by adding hydrogen during production by polymerization to control the molecular weight and polymerization activity. Can be adjusted.
_{The above-mentioned ultimate viscosity [η] is the viscosity increase rate η sp} (that is, η _sp / c) per unit concentration c of each polymer when different amounts of thermoplastic resin compositions are dissolved in decalin at 135 ° C. The reduced viscosity is η _red, and η _red can be extrapolated so that the unit concentration c of the polymer becomes zero.

Requirement (i);
The ratio of the 4-methyl-1-pentene / α-olefin copolymer (A-1) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mn). The molecular weight distribution: Mw / Mn) is preferably 1.0 or more and 3.5 or less. The Mw / Mn is more preferably 1.2 or more and 3.0 or less, and further preferably 1.5 or more and 2.8 or less. The 4-methyl-1-pentene / α-olefin copolymer (A-1) having Mw / Mn in the above range is in the form of a sheet, which is less likely to be deteriorated in moldability due to a low molecular weight and low stereoregular polymer. It is easy to mold into a thermoplastic resin composition.

The weight average molecular weight (Mw) of the 4-methyl-1-pentene / α-olefin copolymer (A-1) measured by gel permeation chromatography (GPC) is 500 or more and 10 in terms of polystyrene. It is preferably less than, million, more preferably 1,000 or more and less than 5,000,000, and even more preferably 1,000 or more and less than 2,500,000.

The Mw / Mn and Mw of the 4-methyl-1-pentene / α-olefin copolymer (A-1) can be adjusted to the above range by using, for example, a metallocene catalyst.
For the above Mw and Mw / Mn, for example, Waters ALC / GPC 150-C plus type (integrated with a differential refractometer detector) is used as a liquid chromatograph, and Toso Co., Ltd. GMH6-HT × 2 and GMH6 are used as columns. -HTL x 2 are connected in series, o-dichlorobenzene is used as the mobile phase medium, and the chromatogram obtained by measuring at a flow rate of 1.0 ml / min and 140 ° C. is obtained using a calibration curve using a standard polystyrene sample. Can be analyzed and obtained.

Requirement (j);
The density of the 4-methyl-1-pentene / α-olefin copolymer (A-1) (measured by JIS K7112) is preferably 870 to 830 kg / m ³ . The density is more preferably 856 to 830 kg / m ³ , still more preferably 855 to 830 kg / m ³ . The details of the measurement conditions and the like are as described in the column of Examples described later.
The density can be appropriately changed depending on the comonomer composition ratio of the copolymer (A-1), and the copolymer (A-1) having a density within the above range is advantageous for producing a lightweight sheet.

Requirement (k);
The melt flow rate (MFR; Melt Flow Rate) of 4-methyl-1-pentene / α-olefin copolymer (A-1) (measured at ASTM D1238 at 230 ° C. under a load of 2.16 kg) is preferable. Is 4.0 to 30 g / 10 min. The melt flow rate is more preferably 7.0 to 15 g / 10 min, still more preferably 7.0 to 13 g / 10 min. The copolymer (A-1) having a melt flow rate within the above range is advantageous in producing good pellets, sheets and molded products during molding.

A particularly preferable form of the 4-methyl-1-pentene / α-olefin copolymer (A-1) further satisfies the above requirement (h) in addition to the above requirements (d) to (g), and is a particularly preferable embodiment. In, in addition to the requirements (d) to (h), one or more, preferably two or more, particularly preferably all selected from the requirements (i), (j) and (k) are satisfied.

<< Method for producing 4-methyl-1-pentene / α-olefin copolymer (A-1) >>
The method for producing the copolymer (A-1) is not particularly limited, but for example, 4-methyl-1-pentene and the above-mentioned "α-olefin leading to the structural unit (ii)" are combined with a magnesium-supported titanium catalyst or a magnesium-supported titanium catalyst. It can be obtained by polymerizing in the presence of a suitable polymerization catalyst such as a metallocene catalyst.

Here, as the polymerization catalyst that can be used in the present invention, conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication No. 01/53369, International Publication No. 01/27124, JP-A-3-193996 or The metallocene catalysts described in JP-A-2-41303, International Publication No. 2011/055803, International Publication No. 2014/050817 and the like are preferably used.

The polymerization can be appropriately selected from a liquid phase polymerization method including dissolution polymerization, suspension polymerization and the like, a gas phase polymerization method and the like.
In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as the solvent constituting the liquid phase. Examples of the above inert hydrocarbons include aliphatic hydrocarbons including propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane and the like. Alicyclic hydrocarbons, including aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons including ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof. included.

Further, in the liquid phase polymerization method, bulk polymerization may be carried out in which the monomer itself that derives the structural unit (i) to the structural unit (iii) is used as a solvent.
The 4-methyl-1-pentene / α-olefin copolymer (A-1) is formed by stepwise copolymerizing the monomers leading from the structural units (i) to the structural units (iii). The composition distribution of the structural unit (i) to the structural unit (iii) can also be appropriately controlled.
The polymerization temperature is preferably −50 ° C. or higher and 200 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and further preferably 20 ° C. or higher and 100 ° C. or lower.

The polymerization pressure is preferably normal pressure or higher and 10 MPa gauge pressure, and more preferably normal pressure or higher and 5 MPa gauge pressure.
At the time of polymerization, hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the polymer to be produced. The amount of hydrogen added is appropriately about 0.001 NL or more and 100 NL or less with respect to 1 kg of the total amount of the monomers leading from the structural unit (i) to the structural unit (iii).

<Carbon-based filler (B)>
The carbon-based filler (B) is a conductive material. Examples thereof include carbon nanotubes (CNTs) and carbon fibers. The carbon-based filler (B) is not particularly limited as long as it is a conductive material, but among these, carbon nanotubes are preferable because they are excellent in the effect of lowering the surface resistivity of the molded product.

The carbon nanotube is a cylindrical hollow fibrous material made of carbon, and may be either a multi-walled carbon nanotube or a single-walled carbon nanotube.
The average diameter of the carbon nanotubes is preferably 1 nm or more, more preferably 5 nm or more, further preferably 7 nm or more, preferably 100 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less. The average length of the carbon nanotubes is preferably 0.5 μm or more, more preferably 0.6 μm or more, preferably 50 μm or less, more preferably 30 μm or less, still more preferably 15 μm or less. If the average diameter is 1 nm or more, it can be made difficult to cut during kneading, and if it is 20 nm or less, the conductivity tends to be improved. Further, if the average length is 0.5 μm or more, the conductivity can be increased, and if it is 50 μm or less, the increase in viscosity during kneading can be suppressed, and kneading and molding tend to be facilitated.

The average diameter and average length of carbon nanotubes can be determined by observing the carbon nanotubes with an electron microscope (SEM, TEM) and arithmetically averaging them.
The carbon nanotubes can be produced by, for example, an arc discharge method, a chemical vapor deposition method (CVD method), or a laser ablation method. Commercially available carbon nanotubes may be used.
Compared to carbon black, for example, carbon nanotubes tend to exhibit high conductivity in a relatively small amount, but since they are expensive, it is advantageous from the viewpoint of cost if they can be used in a smaller amount.

As the carbon fiber, various known carbon fibers can be used, for example, polyacrylic nitrile-based, rayon-based, pitch-based, polyvinyl alcohol-based, regenerated cellulose-based, pitch-based produced from mesophase pitch, and the like. Carbon fiber can be mentioned. Carbon fiber is superior in specific strength in applications where light weight and strength are important, for example, for aircraft.

The carbon fiber may be a general-purpose fiber or a high-strength fiber. Further, the carbon fiber may be a long fiber, a short fiber, a chopped fiber, or a recycled fiber.
As the carbon fiber sizing agent (sizing agent), for example, any sizing agent of urethane-based emulsion, epoxy-based emulsion, nylon-based emulsion, and olefin-based emulsion can be used.

The average length of carbon fibers, that is, the average fiber length is preferably 0.1 mm or more, more preferably 0.3 mm or more, still more preferably 0.5 mm or more, preferably 15.0 mm or less, more preferably 13. It is 0 mm or less. When the average fiber length is 0.1 mm or more, the effect of reinforcing the mechanical properties of the carbon fiber tends to be sufficiently exhibited. When the average fiber length is 15.0 mm or less, the dispersibility of the carbon fibers in the resin composition (X) tends to be good, and thus the appearance tends to be good.

The average diameter of the carbon fibers is preferably 3 μm or more, more preferably 5 μm or more, preferably 30 μm or less, more preferably 21 μm or less, still more preferably 19 μm or less. When the average diameter of the carbon fibers is 3 μm or more, the carbon fibers are less likely to be damaged during molding, and the impact strength of the obtained molded product tends to be high. When the average diameter of the carbon fibers is 30 μm or less, the appearance of the molded product is good, the aspect ratio of the carbon fibers does not decrease, and the molded product is sufficiently reinforced for mechanical properties such as rigidity and heat resistance. It tends to be effective.

One type or two or more types of carbon-based filler (B) can be used.
The content ratio of the carbon-based filler (B) in the resin composition (X) is 0.1 to 20.0 parts by mass, where 100 parts by mass is the total of the thermoplastic resin (A) and the carbon-based filler (B). be. The content ratio of the carbon-based filler (B) is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, further preferably 1.0 part by mass or more, and preferably 15.0 parts by mass. Parts or less, more preferably 10.0 parts by mass or less.

<Other ingredients>
The resin composition may further contain a resin other than the thermoplastic resin (A) and the carbon-based filler (B), and additives for various resins.

≪Other polymers≫
The resin composition (X) of the present invention corresponds to a thermoplastic resin (A) such as 4-methyl-1-pentene / α-olefin copolymer (A-1) as long as the effects of the present invention are not impaired. Other polymers that do not (hereinafter referred to as "other polymers") may be further contained.

Examples of "other polymers" are conventionally known low-density, medium-density, high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, and poly 4-methyl. Examples thereof include resins typified by -1-pentene, poly-3-methyl-1-butene, cyclic olefin copolymers, chlorinated polyolefins, thermoplastic polyurethanes and the like. These resins may be used alone or in combination of two or more.

The blending amount of these resins is preferably 0 to 25 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). be. Here, when producing the resin composition (X), these resins may be used in the form of a composition containing an additive described later, and the blending amount of the resin in that case is the composition. The mass obtained by subtracting the mass of the additive from the mass of is used as a reference.

Further, the "other polymer" is not limited to the unmodified polymer, and may be a modified polymer. From this, the resin composition (X) of the present invention contains a modified polyolefin wax (C) in order to facilitate kneading the carbon-based filler (B) having a high content with the thermoplastic resin (A). It may be included. By using this modified polyolefin wax (C), it is considered that agglomeration of the carbon-based filler (B) in the thermoplastic resin (A) is suppressed, so that kneading becomes easy. Further, it is considered that it becomes easy to knead the carbon-based filler (B) having a high content in the thermoplastic resin (A).

The type of the modified polyolefin wax (C) is not particularly limited, but the modified polyethylene wax and the modified polypropylene wax are preferable, and the modified polyethylene wax is more preferable.
The modified polyolefin wax (C) can be produced by a known method. For example, a method of adding an unsaturated carboxylic acid or a derivative thereof to a low molecular weight ethylene polymer in a solvent-free or solvent by a radical reaction, a method of adding in the presence of Lewis acid, and a method of adding at a high temperature can be mentioned. Be done. The reaction temperature is 20 ° C. to 300 ° C., particularly preferably 120 ° C. to 250 ° C. Since the melting point of the low molecular weight ethylene polymer is about 120 ° C., it is preferable to set the reaction temperature to 120 ° C. or higher in order to make the reaction system uniform.

The unsaturated carboxylic acid is not particularly limited as long as it is a compound having a reactive double bond and a carboxylic acid group, and examples of the usable compound include known unsaturated carboxylic acids. The derivative of the unsaturated carboxylic acid is not particularly limited as long as it is a compound having a reactive double bond and a group that can be derived from the carboxylic acid group. For example, an anhydride or an ester of the unsaturated carboxylic acid. , Acid halide, amide and imide and the like.

Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid, and maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, norbornenedicarboxylic acid, and nagic. Examples thereof include unsaturated dicarboxylic acids such as acid endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid). By using an unsaturated carboxylic acid, a modified hydrocarbon resin having a carboxylic acid group can be obtained.

As the unsaturated carboxylic acid anhydride, the unsaturated dicarboxylic acid anhydride can be used. Specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and endocis anhydride-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride. ) Etc. can be mentioned. By using an anhydride of unsaturated carboxylic acid, a modified hydrocarbon resin having an anhydrous carboxylic acid group can be obtained. Maleic anhydride is particularly preferable.

As the ester of the unsaturated carboxylic acid, the alkyl ester of the unsaturated carboxylic acid, the hydroxyalkyl ester, and the glycidyl ester can be used. Specific examples include monomethyl maleate, dimethyl maleate, glycidyl maleate, hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate. By using an unsaturated carboxylic acid ester, a modified hydrocarbon resin having a carboxylic acid ester group can be obtained.

Specific examples of the unsaturated carboxylic acid halide include malenyl chloride, dichloromaleic anhydride (C ₄ Cl ₂ O ₃ ) and the like. By using an unsaturated carboxylic acid halide, a modified hydrocarbon resin having a halogen atom-containing carboxylic acid group can be obtained.

Specific examples of the unsaturated carboxylic acid amide include sulamide, phthalamide, maleamide and the like. By using an unsaturated carboxylic acid amide, a modified hydrocarbon resin having an amide group can be obtained.

Specific examples of the unsaturated carboxylic acid imide include maleimide, phthalimide, and sulfimide. By using the imide of an unsaturated carboxylic acid, a modified hydrocarbon resin having an imide group can be obtained.

The acid value of the modified polyolefin wax (C) is preferably 1 to 100 mg-KOH / g, more preferably 10 to 90 mg-KOH / g. The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the modified polyolefin wax (C) is preferably 400 to 20000.
The blending amount of the modified polyolefin wax (C) is preferably 0 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.3 to 13 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). It is 10 parts by mass.

≪Additives≫
The resin composition (X) may further contain known additives, if necessary.
Additives include, for example, weathering stabilizers, heat stabilizers, UV absorbers, infrared absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, plasticizers, aging. Examples include, but are not limited to, inhibitors, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, fungicides, antibacterial agents, flame retardants, organic fillers, softeners and the like. These additives may be used alone or in combination of two or more.

Examples of softeners include process oils, lubricating oils, paraffins, liquid paraffins, polyethylene waxes, polypropylene waxes, petroleum-based substances such as petroleum asphalt and vaseline, coal tars including coal tar and coal tar pitch, and castor oil. , Fatty oil including flaxseed oil, rapeseed oil, soybean oil and palm oil, waxes including tall oil, beeswax, carnauba wax and lanolin, ricinolic acid, palmitic acid, stearic acid, 12-stearate hydroxide, montane Fatty acids or metal salts thereof including acids, oleic acids and erucic acids, synthetic polymers including petroleum resins, kumaron inden resins and tactic polypropylene, and ester-based plasticizers containing dioctylphthalate, dioctyl adipate and dioctyl sebacate. , Microcrystalin wax, liquid polybutadiene or modified products or hydrogenated products thereof, and known softeners including liquid thiocol and the like.

Examples of the softening agent include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methylacetylricinolate, etc.), aliphatic dialbon acid esters (adipic acid-propylene glycol-based polyester, etc.), and aliphatic tricarboxylic acids. Examples thereof include esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), petroleum resins, and the like.

Release agents include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened castor oil, etc.), glycol esters of fatty acids, liquid paraffin, etc. Can be mentioned.

Examples of the antioxidant include phenol-based (2,6-di-t-butyl-4-methylphenol, etc.) and polycyclic phenol-based (2,2'-methylenebis (4-methyl-6-t-butylphenol), etc.). , Phosphorus (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate, etc.), amine-based (N, N-diisopropyl-p-phenylenediamine, etc.) antioxidants Can be mentioned.

Examples of flame retardants include ammonium polyphosphate, ethylene bistris (2-cyanoethyl) phosphonium chloride, tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate, tris (3-hydroxypropyl) phosphine oxide and the like. Phosphate and other phosphorus compounds, chlorinated paraffins, chlorinated polyolefins, chlorine-based flame retardants such as perchlorocyclopentadecane, hexabromobenzene, ethylenebisdibromonorbornandicarboxyimide, ethylenebistetrabromophthalimide, tetrabromobisphenol Includes brominated flame retardants such as A derivative, tetrabromobisphenol S, and tetrabromodipentaerythritol, and mixtures thereof.

Examples of the ultraviolet absorber include benzotriazole type, benzophenone type, salicylic acid type, acrylate type and the like.

Examples of the antibacterial agent include a quaternary ammonium salt, a pyridine compound, an organic acid, an organic acid ester, a halogenated phenol, and an organic iodine.

Examples of the surfactant include nonionic, anionic, cationic or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, polyethylene oxide, and fatty acid ester of glycerin. , Pentaerythritol fatty acid ester, sorbit or sorbitan fatty acid ester, polyhydric alcohol alkyl ether, polyhydric alcohol type nonionic surfactant such as aliphatic amide of alkanolamine, etc., and examples thereof include anionic surfactants. For example, sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, phosphate ester salts such as higher alcohol phosphates, etc. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric tenside include amino acid-type double-sided surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine-type amphoteric surfactants such as hydroxyethyl betaine at the time of higher alkyl.

Examples of the antistatic agent include the above-mentioned surfactant, fatty acid ester, and polymer type antistatic agent. Examples of the fatty acid ester include esters of stearic acid and oleic acid, and examples of the high molecular weight antistatic agent include polyether ester amides.

Examples of the pigment include an inorganic content (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and an organic pigment (azolake-based, thioindigo-based, phthalocyanine-based, anthraquinone-based). Examples of the dye include azo type, anthraquinone type, triphenylmethane type and the like. The amount of these pigments and dyes added is not particularly limited, but is usually 5 parts by mass or less, preferably 0.1 to 3 parts by mass, in total with respect to 100 parts by mass of the copolymer (A).

Anti-slip agents include wax (carnauba wax, etc.), higher fatty acid (stearic acid, etc.), training fatty acid salt (calcium stearate, etc.), higher alcohol (stearyl alcohol, etc.), higher fatty acid amide (stearic acid amide, erucic acid amide, etc.). ) Etc. can be mentioned.

The amount of the above-mentioned various additives added is not particularly limited depending on the intended use within a range not impairing the object of the present invention, but is 0.01 to 0.01 to 100 parts by mass of the thermoplastic resin (A), respectively. It is preferably 30 parts by mass.

<Manufacturing of resin composition (X)>
The resin composition (X) is, for example, a dry blend of a thermoplastic resin (A), a carbon-based filler (B) and other components optionally added, followed by a uniaxial or biaxial extruder or a Banbury mixer or. It can be obtained by melt-kneading with a pressure kneader, extruding into strands, and granulating into pellets. The components such as the carbon-based filler (B) and the inorganic filler may be mixed in advance with the resin components such as the thermoplastic resin (A) and used in the form of a masterbatch.

[Molded product]
The molded product of this embodiment contains the above resin composition (X). Specific examples of the molding method include conventionally known polyolefin molding methods, such as extrusion molding, injection molding, film molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, and powder. Known thermal molding methods such as slush molding, calendar molding, foam molding and the like can be mentioned. By processing the resin composition (X), preferably by injection molding, it is possible to obtain a molded product of the present embodiment containing the resin composition (X). As the molded product, a molded product containing the resin composition (X) containing carbon nanotubes as the carbon-based filler (B) is preferable.

The molded product may be a molded product formed from the resin composition (X), or may be a molded product having a portion formed from the resin composition, for example, a surface layer.

Further, the molded product of the present embodiment is also excellent in mechanical properties.
Molds are used in a wide range of applications, from household products such as daily necessities and recreational products to general industrial products and industrial products. For example, home appliance material parts, communication equipment parts, electrical parts, electronic parts, automobile materials, other vehicle parts, ships, aircraft materials, mechanical mechanism parts, building material related parts, civil engineering parts, agricultural materials, power tool parts, food containers. , Films, sheets, textiles, toys, etc.

Automotive materials include, for example, front doors, back doors, sliding doors, front end modules, door modules, fenders, foil caps, gasoline tanks, seats (stuffing, outer material, etc.), belts, ceiling upholstery, compatible tops, armrests, door trims. , Rear package tray, carpet, mat, sun visor, foil cover, tire, mattress cover, airbag, connector, insulation, hanger, hanger band, wire covering material, electrical insulation, paint, coating material, overlay Materials, flooring, corner walls, deck panels, covers, plywood, ceiling boards, dividers, side walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, soundproof boards, heat insulating boards, window materials Can be mentioned.

Examples of home appliance material parts, communication equipment parts, electrical parts, and electronic parts include printers, personal computers, word processors, keyboards, PDAs (small information terminals), headphone stereos, mobile phones, telephones, facsimiles, copying machines, and ECRs (electronics). Office / OA equipment such as formula money registration machines), calculators, electronic notebooks, electronic dictionaries, cards, holders, stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and sardines. AV equipment such as TVs, VTRs, video cameras, radio cassette recorders, tape recorders, mini discs, CD players, speakers, liquid crystal displays; connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor encapsulation materials, electric wires, cables, Examples include transformers, sensors, deflection yokes, distribution boards, watches, and robot materials.

Daily miscellaneous goods include, for example, clothing, curtains, sheets, plywood, synthetic fiber boards, rugs, entrance mats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, bicycles, musical instruments. Life and sports equipment such as.

Next, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.
Various physical properties in Examples and Comparative Examples were measured by the following methods.

〔composition〕
The content (mol%) of each structural unit (4-methyl-1-pentene and α-olefin) in the 4-methyl-1-pentene copolymer (A-1) ^{was measured by 13} C-NMR.
-Measuring device: Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.)
・ Observation nucleus: ¹³ C (125 MHz)
-Sequence: Single pulse proton decoupling-Pulse width: 4.7 μsec (45 ° pulse)
・ Repeat time: 5.5 seconds ・ Cumulative number: 10,000 times or more ・ Solvent: Ortodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent ・ Sample concentration: 55 mg / 0.6 mL
-Measurement temperature: 120 ° C
-Chemical shift reference value: 27.50 ppm

[Ultimate viscosity [η]]
The ultimate viscosity [η] of the copolymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device.
After dissolving about 20 mg of the specific 4-methyl-1-pentene (4MP1) -based copolymer in 25 ml of decalin, the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After adding 5 ml of decalin to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner as above. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) (see Equation 1 below).
[Η] = lim (ηsp / C) (C → 0) ・ ・ ・ Equation 1

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) of the copolymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC: Gel). It was calculated by a standard polystyrene conversion method using Permeation Chromatography).

-Conditions-
Measuring device: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated type, manufactured by Waters)
Column: Two GMH6-HT (manufactured by Tosoh Corporation) and two GMH6-HTL (manufactured by Tosoh Corporation) are connected in series. Eluent: o-dichlorobenzene Column temperature: 140 ° C.
Flow rate: 1.0 mL / min

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the copolymer was measured at 230 ° C. under a load of 2.16 kg according to ASTM D1238. The unit is g / 10 min.

〔density〕
The density of the copolymer was measured according to JIS K7112 (density gradient tube method). This density (kg / m ³ ) was used as an index of lightness.

[Melting point (Tm)]
The melting point (Tm) of the copolymer was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device. Approximately 5 mg of the polymer is sealed in a measuring aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The polymer was held at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min to completely melt the polymer. After standing at −50 ° C. for 5 minutes, the polymer was heated to 200 ° C. at 10 ° C./min for the second time, and the peak temperature (° C.) at the second heating was defined as the melting point (Tm) of the polymer. When a plurality of peaks were detected, the peak detected on the highest temperature side was adopted.

[Dynamic viscoelasticity]
In the measurement of dynamic viscoelasticity, a press sheet having a thickness of 2 mm made of a copolymer or a molded product to be measured is used as a measurement sample, and a strip piece of 45 mm × 10 mm × 2 mm necessary for dynamic viscoelasticity measurement is further used. I cut it out. Using MCR301 manufactured by ANTONPaar, the temperature dependence of dynamic viscoelasticity from -40 to 150 ° C. was measured at a frequency of 10 rad / s, and the loss tangent (tan δ) due to the glass transition temperature was measured in the range of 0 to 40 ° C. ) Is the peak value (maximum value), the temperature (tan δ peak temperature), and the peak value (tan δ peak value) are measured.

[Synthesis Example 1]
<Synthesis of 4-methyl-1-pentene / α-olefin copolymer (A-1)>
300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. It was charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, and the stirrer was rotated.
Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa.

Subsequently, 1 mmol of methylaluminoxane in terms of Al and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance. 0.34 ml of a toluene solution containing butyl-fluorenyl) zirconium dichloride was press-fitted into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.
60 minutes after the start of polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

The resulting polymerization reaction product containing the solvent was then dried under reduced pressure at 100 ° C. for 12 hours to give 36.9 g of a powdered 4-methyl-1-pentene / α-olefin copolymer (A-1). ) (Hereinafter referred to as "copolymer A-1"). Table 1 shows the measurement results of various physical properties of the obtained copolymer A-1. Here, in Table 1, "4MP1" refers to 4-methyl-1-pentene, and "AO" refers to an α-olefin.

The content of 4-methyl-1-pentene in the copolymer A-1 was 72.5 mol%, and the content of propylene was 27.5 mol%. The density of the copolymer A-1 was 839 kg / m ³ . The limit viscosity [η] of the copolymer A-1 is 1.5 dl / g, the weight average molecular weight (Mw) is 337,000, the molecular weight distribution (Mw / Mn) is 2.1, and the melt flow. The rate (MFR) was 11 g / 10 min. The melting point (Tm) of the copolymer A-1 was not observed.

Method for producing molded product The resin and carbon-based filler described in Examples or Comparative Examples were put into the hopper portion of kzw15 manufactured by Technobel Co., Ltd. and melt-kneaded at 200 ° C. to prepare resin composition pellets. After that, the above resin composition pellets were put into a hopper of a 75-ton injection molding machine manufactured by Toshiba Machine Co., Ltd., melted at 200 ° C., and injected into a mold at 40 ° C. at an injection pressure of 50 MPa and a holding pressure of 30 to 40 MPa. Molding was performed to prepare a flat plate molded product (press sheet) having a thickness of 130 mm × 130 mm × 2 mm and a dumbbell-shaped molded product test piece conforming to ASTM D638 Type 4.

Measurement of surface resistivity
The surface resistivity of the molded product was determined as follows.
For the 2.0 mm thick press sheet of the resin composition, room temperature, humidity 50%, applied voltage 10 V, applied by double ring method using a digital ultra-high resistivity / micro ammeter 8340A type manufactured by ADC Co., Ltd. The surface resistivity was measured under the condition of time 60 seconds.

Shrinkage rate The shrinkage rate was calculated by using the press sheet having a thickness of 2 mm as a measurement sample, measuring the difference from the length of the injection die on four sides, and using the dimensional change with respect to the length of the die.

The tensile strength, the tensile strength and the tensile elastic modulus of the tensile elongation molded product were measured by a tensile test using the dumbbell-shaped molded product test piece. The tensile test was carried out using a 5-hanging tensile tester 2005X-5 manufactured by Intesco Co., Ltd. at a test speed of 50 mm / min at 23 ° C. in accordance with ASTM D638.

[Examples 1 to 3]
Carbon nanotube master batch (15 wt% of carbon nanotube NC7000 manufactured by Nanosil Co., Ltd., which is a carbon-based filler (B), and 4-methyl-1-pentene / α-olefin copolymer (A-1), which is a thermoplastic resin (A). ) A master batch containing 85 wt%: a carbon-based filler master batch) and a 4-methyl-1-pentene / α-olefin copolymer (A-1) which is a thermoplastic resin (A) are shown in Table 2. Dry blended with "blending ratio" (parts by mass). From each compounding ratio, the "composition" ratio (mass%) of each component of the resin composition is calculated as shown in Table 2. Next, a resin composition pellet and a test piece for measuring physical properties were prepared by the above-mentioned method. Tensile test, surface resistivity measurement, shrinkage rate measurement and viscoelasticity measurement were carried out using this test piece.

[Comparative Example 1]
The same method as in Example 1 except that the thermoplastic resin (A) 4-methyl-1-pentene / α-olefin copolymer (A-1) was used without using the carbon nanotube masterbatch. A resin composition pellet and a test piece for measuring physical properties were prepared in the above, and a tensile test, a surface resistance measurement, a shrinkage rate measurement, and a viscoelasticity measurement were carried out.

[Comparative Examples 2 and 3]
Instead of the carbon-based filler master batch of carbon nanotubes of Example 1, a carbon-based filler master batch containing 25 wt% of carbon black and 75 wt% of polypropylene (DIC Co., Ltd. P-5050) was used, and each raw material was shown in Table 2. A resin composition pellet and a test piece for measuring physical properties were prepared in the same manner as in Example 1 except for the ratio, and a tensile test, a surface resistance measurement, a shrinkage rate measurement, and a viscoelasticity measurement were carried out.

Table 2 shows the surface resistivity, shrinkage rate, tanδ peak value, tanδ peak temperature, tensile strength and tensile elastic modulus of the molded products obtained in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 2, "CNT" means carbon nanotubes and "CB" means carbon black.

For the following examples and comparative examples, the thermal conductivity and thermal resistance were determined by the following methods.
(Thermal conductivity)
The thermal conductivity of the thermally conductive composition was carried out by the steady-state heat flow metering method. Specifically, the measurement was performed using a measuring instrument GH-1 manufactured by ULVAC Riko Co., Ltd. at a temperature of 30 ° C., a set air pressure for holding a sample of 0.3 MPa, and a test piece shape of 50 mmφ according to ASTM E1530.
(Thermal resistance)
The thermal resistance was calculated from the following formula.
Thermal resistance = test piece thickness / thermal conductivity

[Example 4]
The resin composition according to Example 1 (a resin composition obtained by dry-blending 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and 25 parts by mass of a carbon nanotube masterbatch). Table 3 shows the results of the thermal conductivity measurement and the thermal resistance of the test piece prepared by the above-mentioned method using the above-mentioned method.

[Example 5]
The resin composition according to Example 2 (a resin composition obtained by dry-blending 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and 66 parts by mass of a carbon nanotube masterbatch). Table 3 shows the results of the thermal conductivity measurement and the thermal resistance of the test piece prepared by the above-mentioned method using the above-mentioned method.

[Example 6]
The resin composition according to Example 3 (a resin composition obtained by dry-blending 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and 115 parts by mass of a carbon nanotube masterbatch). Table 3 shows the results of the thermal conductivity measurement and the thermal resistance of the test piece prepared by the above-mentioned method using the above-mentioned method.

[Comparative Example 4]
Table 3 shows the results of thermal conductivity measurement and thermal resistance obtained by the above method for the test piece prepared by the above method using the resin composition described in Comparative Example 1.

[Comparative Example 5]
The resin composition according to Comparative Example 2 (a resin composition obtained by dry-blending 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and 11 parts by mass of a carbon black masterbatch). Table 3 shows the results of the thermal conductivity measurement and the thermal resistance of the test piece prepared by the above-mentioned method using the above-mentioned method.

[Comparative Example 6]
The resin composition according to Comparative Example 3 (a resin composition obtained by dry-blending 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and 43 parts by mass of a carbon black masterbatch). Table 3 shows the results of the thermal conductivity measurement and the thermal resistance of the test piece prepared by the above-mentioned method using the above-mentioned method.

In Table 3, "CNT" means carbon nanotubes and "CB" means carbon black.

Claims (11)

A thermoplastic resin which is an olefin-based copolymer containing a structural unit (i) derived from an α-olefin having 6 to 20 carbon atoms and a structural unit (ii) derived from an α-olefin having 2 to 5 carbon atoms. (A) 80.0 to 99.9 parts by mass and carbon-based filler (B) 0.1 to 20.0 parts by mass (the total of the thermoplastic resin (A) and the carbon-based filler (B) is 100 parts by mass. The resin composition (X), which comprises the above and satisfies the following requirements (a) to (c):
Requirement (a); The temperature at which the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C is 0 ° C or higher. It is 60 ° C. or lower.
Requirement (b); The peak value of the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C. is 0.5 or more. It is 0 or less.
Requirement (c); The surface resistivity is 10 ^ 14Ω or less. 80.0 to 99.9 parts by mass of the thermoplastic resin (A) and 0.1 to 20.0 parts by mass of the carbon-based filler (B) (the total of the thermoplastic resin (A) and the carbon-based filler (B) is 100. The resin composition (X), which comprises (part by mass) and satisfies the following requirements (a) to (c):
Requirement (a); The temperature at which the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C is 0 ° C or higher. It is 60 ° C. or lower.
Requirement (b); The peak value of the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150 ° C. is 0.5 or more. It is 0 or less.
Requirement (c); The surface resistivity is 10 ^ 14Ω or less. The thermoplastic resin (A) is a 4-methyl-1-pentene / α-olefin copolymer (A-1) in which the α-olefin having 6 or more and 20 or less carbon atoms is 4-methyl-1-pentene. The resin composition (X) according to claim 1, wherein the resin composition (X) is provided. The resin composition (X) according to claim 3, wherein the 4-methyl-1-pentene / α-olefin copolymer (A-1) satisfies the following requirements (d) to (g). :
Requirement (d); The copolymer (A-1) is a structural unit (i) derived from 4-methyl-1-pentene and a structural unit (ii) derived from an α-olefin having 2 or more and 5 or less carbon atoms. Assuming that the total of the above is 100 mol%, the constituent unit (i) 55 to 90 mol% and the constituent unit (ii) 10 to 45 mol% are included.
Requirement (e); The copolymer (A-1) has a melting point (Tm) of 160 ° C. or less as measured by a differential scanning calorimeter (DSC) or a melting point measured by a differential scanning calorimeter (DSC). Not done.
Requirement (f); Copolymer (A-1) is 10 rad / s in the temperature range of -40 to 150 ° C.
The temperature at which the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of (1.6 Hz) has a peak value is 15 ° C. or higher and 45 ° C. or lower.
Requirement (g); Copolymer (A-1) is 10 rad / s in the temperature range of -40 to 150 ° C.
The peak value of the loss tangent tan δ obtained by performing dynamic viscoelasticity measurement at a frequency of (1.6 Hz) is 0.6 or more and 5.0 or less. The resin composition (X) according to any one of claims 1 to 4, wherein the carbon-based filler (B) is a carbon nanotube. A molded product containing the resin composition (X) according to any one of claims 1 to 5. A sheet containing the resin composition (X) according to any one of claims 1 to 5. A toy containing the resin composition (X) according to any one of claims 1 to 5. Daily sundries containing the resin composition (X) according to any one of claims 1 to 5. An automobile material containing the resin composition (X) according to any one of claims 1 to 5. An electronic component containing the resin composition (X) according to any one of claims 1 to 5.