JP2016037581A - Resin composition and method for producing the same - Google Patents

Abstract

A resin composition having a high level of thermal conductivity and insulation, and having excellent impact resistance, rigidity, and heat resistance, and a method for producing the same are provided. A dispersed phase comprising an anisotropic nanofiller (A) and two or more kinds of resins (B) and formed by one kind of resin (B1) of the two or more kinds of resins (B). A resin composition comprising resin particles and a continuous phase formed of the remaining one or more types of resins (B2), wherein the dispersed phase resin particles have an average particle diameter (number average) of 2 μm or less, The anisotropic nanofiller (A) contains a connection structure that exists over two or more dispersed phase resin particles, and forms the connection structure for the total anisotropic nanofiller (A). A resin composition, wherein the ratio (number basis) of the anisotropic nanofiller (A) is 10% or more. [Selection] Figure 1

Description

  The present invention relates to a resin composition containing an anisotropic nanofiller and a method for producing the same.

  Anisotropic nanofillers represented by carbon nanotubes and the like are excellent in various properties such as thermal conductivity and rigidity. By adding this to the resin, these properties can be imparted to or improved in the resin. To be considered. However, when the amount of the anisotropic nanofiller added to the resin is small, it is difficult to greatly improve the thermal conductivity and rigidity. There was a problem that the insulating property was lowered.

  In JP-A-2005-54094 (Patent Document 1), as a resin composition whose thermal conductivity is improved by adding a relatively small amount of anisotropic nanofiller, fibrous carbon or the like is a mixture of two or more kinds of resins. A thermally conductive resin material dispersed therein has been proposed. In this resin material, carbon is selectively dispersed only in one kind of resin phase to form a heat conduction path made of carbon, and thus the heat conductivity is enhanced. It also acts as a path and improves electrical conductivity. For this reason, this resin material cannot be applied to applications that require thermal conductivity (heat dissipation) and insulation.

  Therefore, JP 2011-184681 A (Patent Document 2) discloses a conductive composition as a resin composition capable of improving thermal conductivity while maintaining insulation even when a conductive nanofiller is used. There has been proposed a resin composition in which nanofillers are localized in a dispersed phase and a compound having a functional group is arranged at the interface between the dispersed phase and the continuous phase. However, in this resin composition, it is necessary to enclose anisotropic conductive nanofillers in the dispersed phase, and it is necessary to make the dispersed phase relatively large. For this reason, in this resin composition, sufficient impact resistance, rigidity and heat resistance may not be obtained.

  In addition, in applications such as various parts for automobiles and aircraft, various parts for electrical and electronic equipment, weight reduction and higher functionality of materials are required from the viewpoint of reducing carbon dioxide emissions and energy saving. There has been a demand for a resin material that has high thermal conductivity, impact resistance, rigidity, heat resistance, and insulation properties by adding a small amount of anisotropic nanofiller.

JP 2005-54094 A JP 2011-184681 A

  The present invention has been made in view of the above-mentioned problems of the prior art, has a high level of thermal conductivity and insulation, and further has a resin composition excellent in impact resistance, rigidity and heat resistance, and its An object is to provide a manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have mixed an anisotropic nanofiller and two or more resins in the presence of a compound having a functional group at a high shear rate. In the resin composition comprising an anisotropic nanofiller and two or more kinds of resins and comprising dispersed phase resin particles formed of one kind of resin and a continuous phase formed of the remaining resin, FIG. The components of each phase in the figure depict the main component, and the components in each phase of the resin composition of the present invention are not limited to this. It is found that a connection structure in which nano fillers exist over two or more dispersed phase resin particles is formed, and the resin composition containing such a connection structure has thermal conductivity and insulation properties. Combined at a high level, with excellent impact resistance, rigidity and heat resistance It found that are, and have completed the present invention.

That is, the resin composition of the present invention contains an anisotropic nanofiller (A) and two or more kinds of resins (B), and one kind of resin (B1) among the two or more kinds of resins (B). A resin composition comprising dispersed phase resin particles formed by the above and a continuous phase formed by the remaining one or more types of resins (B2),
The dispersed phase resin particles have an average particle size (number average) of 2 μm or less,
A single anisotropic nanofiller (A) contains a connecting structure that exists over two or more dispersed phase resin particles,
The ratio (number basis) of the anisotropic nanofiller (A) forming the connection structure to the total anisotropic nanofiller (A) is 10% or more.

In the resin composition of the present invention, the resin (B1) is a resin (B _aff ) having the highest affinity with the anisotropic nanofiller (A) of the two or more types of resins (B). It is preferable. Moreover, it is preferable that the resin composition of this invention further contains the compound (C) which has a functional group.

Moreover, the manufacturing method of the resin composition of this invention contains anisotropic nano filler (A) and 2 or more types of resin (B), and is 1 type of resin of the said 2 or more types of resin (B). A method for producing a resin composition comprising dispersed phase resin particles formed by (B1) and a continuous phase formed by one or more remaining resins (B2),
By mixing the anisotropic nanofiller (A), the resin (B1), the resin (B2) and the compound (C) having a functional group under a shear rate of 200 s ⁻¹ or more,
Forming the dispersed phase resin particles having an average particle diameter (number basis) of 2 μm or less,
A single anisotropic nanofiller (A) forms a connected structure in which two or more dispersed phase resin particles exist,
The connection structure is formed on 10% or more (several standards) of the total anisotropic nanofiller (A).

  Although the reason why the resin composition of the present invention is excellent in impact resistance by containing a connecting structure as shown in FIG. 1 is not necessarily clear, the present inventors have as follows. I guess. That is, in the resin composition of the present invention, the anisotropic nanofiller (A) 1 forms a connected structure with the dispersed phase resin particles 2 formed of the resin (B1), and thus is melt-kneaded or molded. Re-aggregation of anisotropic nanofillers (A) 1 due to van der Waals forces during processing is inhibited by the presence of dispersed phase resin particles 2, and the highly dispersed state of anisotropic nanofillers (A) 1 is maintained. Is done. The dispersed phase resin particles 2 form a strong interface with both the continuous phase 3 formed of the resin (B2) and the anisotropic nanofiller (A) 1. In the resin composition of the present invention, since the anisotropic nanofiller (A) 1 is present over a plurality of such dispersed phase resin particles 2, even when an external force is applied to the resin composition, it is different. It is not easy to draw the isotropic nanofiller (A) 1 from the plurality of dispersed phase resin particles 2. For this reason, it is presumed that a lot of energy is required to extract the anisotropic nanofiller (A) 1 and the impact resistance is improved. In addition, the dispersed phase resin particles 2 form a strong interface with the anisotropic nanofiller (A) 1 and the crystallinity of the dispersed phase resin particles 2 is enhanced by the nucleating agent effect of the anisotropic nanofiller (A) 1. Therefore, the resin composition of the present invention is presumed to be excellent in thermal conductivity, rigidity, and heat resistance.

  According to the present invention, it is possible to obtain a resin composition having both high thermal conductivity and insulating properties and excellent in impact resistance, rigidity, and heat resistance.

It is a schematic diagram which shows one embodiment of the resin composition of this invention containing an anisotropic nano filler. 2 is a transmission electron micrograph showing the resin composition obtained in Example 1. FIG. 2 is a transmission electron micrograph showing the resin composition obtained in Comparative Example 1.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the resin composition of the present invention will be described. The resin composition of the present invention contains an anisotropic nanofiller (A) and two or more kinds of resins (B). In this resin composition, dispersed phase resin particles are formed by one type of resin (B1) of the two or more types of resins (B), and a continuous phase is formed by the remaining one or more types of resins (B2). Has been. Moreover, the single said anisotropic nano filler (A) exists over two or more said dispersed phase resin particles, and forms the connection structure.

  First, the anisotropic nanofiller (A) used in the present invention, two or more kinds of resins (B), and the compound (C) having a functional group will be described.

(A) Anisotropic nanofiller Although there is no restriction | limiting in particular as an anisotropic nanofiller (A) used for this invention, For example, anisotropic carbon type | system | group nanofiller, anisotropic metal type | system | group nanofiller, metal, Anisotropic conductive nanofillers such as anisotropic nanofillers coated with a conductive polymer or the like, anisotropic boron nitride-based nanofillers, and the like are preferable. These anisotropic nanofillers may be used alone or in combination of two or more. Among such anisotropic nanofillers, anisotropic conductive nanofillers are preferred from the viewpoint of improving thermal conductivity and mechanical strength, and anisotropic carbon-based nanofillers and anisotropic metal-based nanofillers are preferred. More preferred is an anisotropic carbon-based nanofiller.

  The anisotropic carbon-based nanofiller is not particularly limited as long as it is an anisotropic carbon-based nanofiller, but from the viewpoint of improving thermal conductivity and mechanical strength, carbon nanofiber, carbon nanohorn, carbon nano Cone, carbon nanotube, carbon nanocoil, carbon microcoil, carbon nanochaplet, graphite, graphene, graphene nanoribbon, graphene nanodot, graphene nanoplatelet, and derivatives thereof are preferred, carbon nanofiber, carbon nanotube, graphite, graphene, Graphene nanoribbons, graphene nanodots, and graphene nanoplatelets are more preferable, and carbon nanofibers and carbon nanotubes are particularly preferable. These anisotropic carbon-based nanofillers may be used alone or in combination of two or more. In addition, the anisotropic carbon-based nanofiller may contain atoms, molecules, and the like other than carbon, and may contain a metal or other nanostructure as necessary.

In the present invention, the peak of the Raman spectrum obtained by measuring the anisotropic carbon-based nanofiller with a Raman spectrophotometer is observed in the vicinity of about 1585 cm ⁻¹ due to the displacement vibration of the carbon atom in the graphene structure. There is no particular limitation on the ratio (G / D) of the G band to be observed and the D band (G / D) observed in the vicinity of about 1350 cm ⁻¹ where it is observed that there is a defect in the graphene structure. Is preferably 0.1 or more, more preferably 1.0 or more, still more preferably 3.0 or more, particularly preferably 5.0 or more, and most preferably 10.0 or more. When G / D is less than the lower limit, thermal conductivity tends not to be sufficiently improved.

  In addition, when carbon nanotubes and / or carbon nanofibers are used as the anisotropic nanofiller (A), either single-walled or multi-layered (two or more layers) can be used. Or can be used together.

  Such an anisotropic carbon-based nanofiller may be produced by appropriately applying a conventionally known production method such as a laser ablation method, an arc synthesis method, a chemical vapor deposition method (CVD method) such as a HiPco process, or a melt spinning method depending on the application. Although it can manufacture by selecting, it is not limited to what was manufactured by these methods.

  Examples of the anisotropic metal-based nanofiller used in the present invention include anisotropic metal fillers and anisotropic fillers of metal compounds such as metal oxides and metal hydroxides. There is no particular limitation on the metal constituting such an anisotropic metal-based nanofiller, for example, silver, copper, gold, brass, aluminum, iron, platinum, tin, magnesium, molybdenum, rhodium, zinc, palladium, Tungsten, chromium, cobalt, nickel, titanium, metallic silicon, and alloys thereof are preferable. Of these metals, silver, copper, gold, brass, aluminum, iron, platinum, tin, and alloys and oxides thereof are preferable from the viewpoint of improving thermal conductivity. Furthermore, in addition to thermal conductivity, such a metal can impart a function specific to each metal (for example, antibacterial action in the case of silver) to the resin composition. The shape of such an anisotropic metal-based nanofiller is not particularly limited as long as it has anisotropy, and examples thereof include a flat plate shape, a rod shape, a fiber shape, and a tube shape.

  Moreover, there is no restriction | limiting in particular as an anisotropic nanofiller coat | covered with the metal used for this invention, a conductive polymer, etc. For example, the glass bead coat | covered with metals, such as silver, copper, gold | metal | money, polyaniline, polypyrrole Glass beads coated with a conductive polymer such as polyacetylene, poly (paraphenylene), polythiophene or polyphenylene vinylene are preferred.

  The anisotropic boron nitride nanofiller used in the present invention is not particularly limited, and for example, boron nitride nanotubes, hexagonal boron nitride, boron nitride nanosheets, boron nitride nanodots, and the like are preferable.

  In the present invention, as the anisotropic nanofiller (A), an anisotropic nanofiller such as the anisotropic carbon-based nanofiller, anisotropic metal-based nanofiller, or anisotropic boron nitride-based nanofiller is used. In the structure, a carboxyl group, a nitro group, an amino group, an alkyl group, a substituent such as an organic silyl group, a polymer such as poly (meth) acrylate ester, the conductive polymer or the like introduced by chemical bonding, A material obtained by coating the anisotropic nanofiller with another conductive material can be used.

  Although there is no restriction | limiting in particular as a shape of the anisotropic nano filler (A) used for this invention, From a viewpoint of improvement of thermal conductivity, impact resistance, rigidity, and heat resistance, rod shape, fiber shape, tube shape, A flat plate shape, a coil shape, a conical shape and the like are preferable.

  Further, the aspect ratio of the anisotropic nanofiller (A) used in the present invention is not particularly limited, but when mixed with a resin, mechanical strength such as tensile strength and impact strength of the resin composition can be added in a small amount. From the viewpoint of improving thermal conductivity, 3 or more is preferable, 5 or more is more preferable, 10 or more is more preferable, 20 or more is particularly preferable, and 40 or more is most preferable. Here, in the present invention, the aspect ratio represents the ratio of the length to the diameter when the anisotropic nanofiller (A) has a so-called one-dimensional structure such as a rod shape, a fiber shape, or a tube shape. In the case of a flat plate, so-called two-dimensional structure, it represents the ratio of the length of the long side of the two-dimensional plane to the thickness (the length of the longest edge among the edges of the plane). Represents the ratio of the length of the coil to the outer diameter of the coil, and in the case of a conical shape, the ratio of the length (height) to the maximum diameter portion.

  When the shape of the anisotropic nanofiller (A) used in the present invention is rod-shaped, fibrous, tube-shaped or conical, the average diameter (in the case of conical shape, the average diameter of the maximum diameter portion) is not particularly limited. However, from the viewpoint of improving thermal conductivity and rigidity, it is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 100 nm or less. When the average diameter of the anisotropic nanofiller (A) exceeds the upper limit, even if the anisotropic nanofiller (A) is added to the resin, the addition of a small amount does not sufficiently improve the thermal conductivity, or the bending elasticity. There is a tendency that the mechanical strength such as rate is not sufficiently developed. In addition, although there is no restriction | limiting in particular as a lower limit of the average diameter of anisotropic nanofiller (A), 0.3 nm or more is preferable and 0.4 nm or more is more preferable.

  When the shape of the anisotropic nanofiller (A) used in the present invention is planar, the average thickness is not particularly limited, but is preferably 500 nm or less, and preferably 100 nm or less from the viewpoint of improving thermal conductivity and rigidity. Is more preferably 50 nm or less, particularly preferably 20 nm or less, and most preferably 10 nm or less. The lower limit of the average thickness of the anisotropic nanofiller (A) is not particularly limited, but is preferably 0.3 nm or more.

  In the resin composition of the present invention, the lower limit of the content of the anisotropic nanofiller (A) is not particularly limited, but is 0 with respect to 100% by volume of the resin composition (hereinafter referred to as “the entire resin composition”). 0.1% by volume or more is preferable, 0.3% by volume or more is more preferable, 0.5% by volume or more is further preferable, 0.7% by volume or more is particularly preferable, and 1.0% by volume or more is most preferable. When the content of the anisotropic nanofiller (A) is less than the lower limit, thermal conductivity and rigidity tend to decrease. Moreover, there is no restriction | limiting in particular as an upper limit of content of an anisotropic nanofiller (A), However 90 volume% or less is preferable with respect to the whole resin composition, 70 volume% or less is more preferable, and 50 volume% or less is preferable. More preferred is 30% by volume or less, and most preferred is 20% by volume or less. When the content of the anisotropic nanofiller (A) exceeds the upper limit, the moldability of the resulting resin composition tends to be lowered.

  In the resin composition of the present invention, such anisotropic nanofiller (A) is usually formed of two or more of the two or more kinds of resins (B) formed of one kind of resin (B1). Present in the dispersed phase resin particles to form a connected structure (particularly, in the case where the anisotropic nanofiller (A) has a one-dimensional structure, a skewed structure is formed). However, it does not preclude that a part of the dispersed phase resin particles are present in the continuous phase, and if a part of the dispersed phase resin particles are coarsened, it is present in the coarse dispersed phase resin particles. It is not a hindrance.

(B) Resin In the present invention, two or more (preferably two) resins are used. Examples of such resin (B) include epoxy resin, phenol resin, melamine resin, thermosetting imide resin, thermosetting polyamideimide, thermosetting silicone resin, urea resin (urea resin), and unsaturated polyester resin. Thermosetting resins such as benzoguanamine resin, alkyd resin, cyanate resin, urethane resin, and diallyl phthalate resin; polystyrene, AS (acrylonitrile-styrene) resin, methyl methacrylate-acrylonitrile-styrene resin, poly (meth) acrylate methyl , Acrylic resins such as poly (meth) acrylic acid ethyl, poly (meth) acrylic acid propyl, poly (meth) acrylic acid butyl, poly (meth) acrylic acid, and copolymers thereof, polyacrylonitrile, acrylonitrile-acrylic Acid methyl resin and Vinyl cyanide resin such as acrylonitrile-butadiene resin, imide ring-containing vinyl polymer, polyolefin resin, acid anhydride-modified acrylic elastomer, epoxy-modified acrylic elastomer, silicone resin, polycarbonate, cyclic polyolefin, polyamide, polyethylene terephthalate , Polyester resins such as polybutylene terephthalate and poly 1,4-cyclohexanedimethyl terephthalate, polyarylate, liquid crystal polyester, polyarylene ether (including modified polyarylene ether), polyarylene sulfide such as polyphenylene sulfide, polysulfone, polyether Sulfone, polyoxymethylene, polytetrafluoroethylene, fluorinated ethylene propylene, polychlorotrif Fluoropolymers represented by polyethylene, polyvinylidene fluoride and polyvinyl fluoride, polylactic acid, polyvinyl chloride, thermoplastic polyimide, thermoplastic polyamideimide, polyetherimide, polyetheretherketone, polyetherketoneketone, polyetheramide, Examples thereof include thermoplastic resins such as polycyclic aromatic group-containing polymers.

  In the resin composition of the present invention, among the two or more kinds of resins (B), dispersed phase resin particles are formed by part or all of one kind of resin (B1), and the remaining one or more kinds of resin (B1). A continuous phase is formed by a part or all of the resin (B2) (hereinafter referred to as “other resin (B2)”). A resin composition comprising such dispersed phase resin particles and a continuous phase is excellent in insulation.

In the resin composition of the present invention, as the resin (B1), a resin (B _aff ) having the highest affinity with the anisotropic nanofiller (A) of the two or more types of resins (B). (Hereinafter referred to as “high affinity resin (B _aff )”) is preferably used. Thereby, in the resin composition of this invention, the said connection structure forms favorably and exists in the tendency for thermal conductivity, insulation, impact resistance, rigidity, and heat resistance to improve. The combination of the high affinity resin (B _aff ) and the other resin (B2) is determined by the affinity between the two or more types of resins (B) to be used and the anisotropic nanofiller (A). is there.

In the present invention, “the resin (B _aff ) having the highest affinity with the anisotropic nanofiller (A)” is the affinity with the anisotropic nanofiller (A) among the two or more types of resins (B). This resin has the highest properties. The high affinity resin (B _aff ) is, for example, the most in the case where two or more kinds of resins are melt-kneaded by the same volume (unit: volume%) and mixed with the anisotropic nanofiller (A). It refers to a resin containing an amount (unit: volume%) of anisotropic nanofiller (A). Such a high affinity resin (B _aff ) is not particularly limited as long as it has the highest affinity with the anisotropic nanofiller (A) among the two or more types of resins (B). For example, among two or more kinds of resins (B), a functional having a smaller interfacial energy between the anisotropic nanofiller (A), a higher flexibility, a higher crystallinity, and a higher electron withdrawing property. Anisotropic nanofiller (A) having a structure showing an interaction such as π-π interaction, CH-π interaction, and π-cation interaction with anisotropic nanofiller (A) having a group When it has a functional group such as a carboxyl group, a resin having at least one characteristic such as an interaction such as a hydrogen bond is preferable, and it has two or more of these characteristics. A resin is more preferable.

Specifically, two types of resins (B) each having 1% by volume and 49.5% by volume of anisotropic nanofiller (A) are mixed in a precision same-direction biaxial kneader (manufactured by Thermo Fisher Scientific Co., Ltd.). Micro rheology compounder HAAKE-MiniLab ") and melt kneading for 5 minutes at a screw rotation speed of 200 rpm at a temperature of the melting point of the resin having the higher melting point of the two types of resins (B) + 20 ° C. in a nitrogen atmosphere. Do. About the obtained resin composition, press molding is performed at the temperature of melting | fusing point +20 degreeC of resin which has higher melting | fusing point of 2 types of resin (B), and a 2 mm-thick molded article is produced. A sample of 40 mm × 5 mm × 2 mm is cut out from this molded product, and an arbitrary portion of the central portion (portion in the range of 0.8 to 1.2 mm from the surface) of the frozen fracture surface at the center of this sample is scanned. Photographed using a scanning electron microscope (SEM) and developed on a photographic paper having a uniform thickness. In the obtained SEM photograph, the range of 90 μm × 90 μm in the size of the molded product is randomly extracted at three locations. After measuring the mass of the photograph of the extracted range, all the parts corresponding to the anisotropic nanofiller (A) in the extraction range are cut out, and the total mass of the photograph of the cut-out part is measured. Moreover, the mass of the photograph of the part corresponding to the anisotropic nanofiller (A) contained in each resin among the parts corresponding to the anisotropic nanofiller (A) was measured, and the extraction range The mass ratio (mass%) of the photograph of the anisotropic nanofiller (A) in each resin with respect to the total anisotropic nanofiller (A) is calculated. This evaluation is performed for the above three extraction ranges, the average value thereof is obtained, and the one with the higher average value (mass%) of the mass ratio of the anisotropic nanofiller (A) in each resin has the higher affinity. Defined as a conductive resin (B _aff ).

  Of the resins exemplified as the two or more kinds of resins (B), the resins suitably used as the resin (B1) include polyolefin resins, polyarylene sulfides, polyester resins, resins containing nitrogen atoms, and Polycyclic aromatic group-containing polymers are mentioned, among them, from the viewpoint of high affinity with the anisotropic nanofiller (A) and improving the thermal conductivity and rigidity of the resulting resin composition, Polyarylene sulfide, polyester resin, polyamide, imide ring-containing vinyl polymer, polyimide, polyetherimide, polyamideimide, and polycyclic aromatic group-containing polymer are preferred, polyolefin resin, polyarylene sulfide, polyester resin, Polyamide and imide ring-containing vinyl polymer are more preferable, and the resulting resin From the viewpoint of improving the heat resistance of Narubutsu, polyarylene sulfide, polyester resins, polyamides and imide ring-containing vinyl polymer is particularly preferred.

  Of the two or more resins (B) used in the present invention, the other resin (B2) other than the resin (B1) is not particularly limited, and among those exemplified as the resin (B), Resins other than those used as the resin (B1) can be suitably used. From the viewpoint of improving the thermal conductivity of the resulting resin composition, for example, aromatic vinyl resins, acrylic resins, polycarbonates Polyarylene sulfide, polyamide, polyester resin, imide ring-containing vinyl polymer and the like are preferable.

  The polyolefin resin used in the present invention may be either linear or branched. The polyolefin resin is not particularly limited, and examples thereof include homopolymers and copolymers of olefin monomers. Examples of the olefin monomers include ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, and 3-methyl-1. -Monoolefin monomers such as butene, 2,3-dimethyl-2-butene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene; 1,2-propadiene, methylallene, butadiene, isoprene 2,3-dimethylbutadiene, 1,3-pentadiene, 1,4-pentadiene, dicyclopentadiene, chloroprene, 1,5-hexadiene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2 -Diene monomers such as norbornene and halides thereof. These olefinic monomers may be used alone or in combination of two or more.

  Specific examples of such olefin monomer copolymers include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-1-hexene. Copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-vinyl-2-norbornene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1,4 -Cyclohexadiene copolymer, polystyrene-poly (ethylene / propylene) block copolymer (SEP), polystyrene-poly (ethylene / propylene) -polystyrene block copolymer (SEPS), polystyrene-poly (ethylene / butylene) polystyrene Block copolymer (SEBS), polystyrene Ethylene-based copolymers such as poly (ethylene-ethylene / propylene) -polystyrene block copolymer (SEEPS) and ethylene-1-octene copolymer; propylene-1-butene-4-methyl-1-pentene copolymer And propylene-based copolymers such as propylene-1-butene copolymer; styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene-styrene (ABS) Resin, (meth) acrylic acid methyl-acrylonitrile-butadiene-styrene (MABS) resin, 1-hexene-4-methyl-1-pentene copolymer, 4-methyl-1-pentene-1-octene copolymer, etc. Can be mentioned. Moreover, the modified material which introduce | transduced functional groups, such as an acid and / or an acid anhydride group, an epoxy group, into the said polyolefin resin can also be used. When a polypropylene resin is used as the polyolefin resin, any polypropylene resin such as isotactic, atactic and syndiotactic can be used as the polypropylene resin.

  Among such polyolefin resins, polyethylene resins (ethylene homopolymers and copolymers) are preferred from the viewpoint of high affinity with the anisotropic nanofiller (A), and ethylene homopolymers and An ethylene-1-butene copolymer is more preferred. Examples of the ethylene homopolymer include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), or Ultra Low Density Polyethylene. (ULDPE)), ultrahigh molecular weight polyethylene (UHMW-PE, generally having a molecular weight of 1,500,000 or more) and the like, and HDPE is particularly preferable from the viewpoint of high thermal conductivity.

  Although there is no restriction | limiting in particular as specific gravity of the polyolefin resin used for this invention, 0.85 or more are preferable, 0.90 or more are more preferable, 0.94 or more are further more preferable, 0.95 or more are especially preferable, 0 .96 or more is most preferable. If the specific gravity of the polyolefin resin is less than the lower limit, the thermal conductivity tends to be difficult to improve sufficiently.

  Moreover, there is no restriction | limiting in particular as melt flow rate (measured at 190 degreeC based on MFR and JISK6922-1) in the case of using as said resin (B1), From a viewpoint of a moldability improvement It is preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more, further preferably 0.3 g / 10 min or more, particularly preferably 0.4 g / 10 min or more, and most preferably 0.5 g / 10 min or more. Further, from the viewpoint of forming more stable dispersed phase resin particles and improving insulation, 100 g / 10 min or less is preferable, 90 g / 10 min or less is more preferable, and 80 g / 10 min or less is more preferable. If the MFR of the polyolefin-based resin is less than the lower limit, the fluidity of the resulting resin composition tends to decrease, and if it exceeds the upper limit, the insulating property tends to decrease.

  As the polyarylene sulfide used in the present invention, conventionally known polyarylene sulfides can be used. For example, any of linear polyarylene sulfides, crosslinked polyarylene sulfides, and mixtures thereof can be used. Among such polyarylene sulfides, p-phenylene sulfide homopolymer and m-phenylene sulfide (co) polymer are preferable.

As the melt viscosity (temperature 310 ° C., shear rate 1200 sec ⁻¹ ) of polyarylene sulfide when used as the resin (B1), it is easy to form dispersed phase resin particles, easily form a connected structure, and From the viewpoint of improving the insulation as a result of these, it is preferably 2 Pa · s or more, more preferably 5 Pa · s or more, further preferably 10 Pa · s or more, particularly preferably 20 Pa · s or more, most preferably 50 Pa · s or more. preferable.

  Although there is no restriction | limiting in particular as a polyester-type resin used for this invention, The resin obtained by a polycondensation reaction using a polyhydric alcohol and polyhydric carboxylic acid as a raw material is mentioned. The number average molecular weight in terms of polystyrene by GPC analysis of the tetrahydrofuran-soluble component (hereinafter referred to as “THF-soluble component”) of such a polyester-based resin is not particularly limited, but is usually preferably 1,000 to 100,000. 2,000 to 50,000 are more preferable, and 3,000 to 30,000 are still more preferable.

  The polyhydric alcohol is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, Dihydric alcohols such as bisphenol A, hydrogenated bisphenol A, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, such as glycerin, sorbitol, 1,4-sodium Tail, 2-methylpropane triol, trimethylol ethane, and a trivalent or higher alcohols such as trimethylolpropane. Among these, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A Of these, propylene oxide adducts are preferred. These polyhydric alcohols may be used alone or in combination of two or more.

  Moreover, although it does not specifically limit as said polyhydric carboxylic acid, For example, aliphatic dicarboxylic acid and aromatic dicarboxylic acid are mentioned. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Examples include 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid and the like. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, and mesaconic acid. In addition, derivatives such as dibasic acid salts and acid anhydrides of these dicarboxylic acids and alkyl esters having 1 to 16 carbon atoms can also be used. Of these, adipic acid, isophthalic acid, terephthalic acid and the like are preferable. These polyvalent carboxylic acid components may be used alone or in combination of two or more.

  Examples of the polyamide used in the present invention include homopolymers and copolymers obtained mainly from at least one of amino acids, lactams and diamines and dicarboxylic acid. Such a polyamide can be obtained by a known polycondensation reaction. The molecular weight of such a polyamide is not particularly limited, but the relative viscosity of a solution obtained by dissolving polyamide in 96% concentrated sulfuric acid at a concentration of 1 g / dl is preferably 1.5 or more at 25 ° C. It is more preferably 8 or more, further preferably 1.9 or more, particularly preferably 2.0 or more, preferably 5.0 or less, and 4.5 or less. Is more preferable. When the relative viscosity is less than the lower limit, the mechanical strength of the resulting resin composition tends to decrease, and when the upper limit is exceeded, the fluidity of the resin composition tends to decrease.

  Examples of the amino acid include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, and examples of the lactam include ε-caprolactam and ω-laurolactam. As tetramethylenediamine, hexamethylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, nonanediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexa 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) ) Aliphatic, alicyclic or aromatic diamines such as methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine.

  Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, Examples thereof include aliphatic, alicyclic or aromatic dicarboxylic acids such as 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

  Specific examples of such polyamides include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyundecanamide (nylon 11), polydodecanamide (Nylon 12), polyhexamethylene sebacamide (nylon 610), polyhexamethylene azelamide (nylon 69), polyhexamethylene terephthalamide (nylon 6T), nylon 9T, nylon MXD6, nylon 6/66 copolymer, polycapro Amide / polyhexamethylene sebacamide copolymer (nylon 6/610 copolymer), nylon 6 / 6T copolymer, nylon 6/66/610 copolymer, nylon 6/12 copolymer, nylon 6T / 12 copolymer, nylon 6 / 66 copolymer, polycaproamide / polyhexamethylene isophthalamide copolymer (nylon 6 / 6I copolymer), nylon 66 / 6I / 6 copolymer, nylon 6T / 6I copolymer, nylon 6T / 6I / 66 copolymer, nylon 6/66/610 / 12 copolymer, nylon 6T / M-5T copolymer and the like. Among them, from the viewpoint of high affinity with the anisotropic nanofiller (A), the polyamide for forming the dispersed phase resin particles is preferably a polyamide having an aromatic group, such as nylon 6T, nylon 9T, nylon MXD6. , Nylon 6 / 6T copolymer, nylon 6T / 12 copolymer, nylon 6T / 66 copolymer, nylon 6 / 6I copolymer, nylon 66 / 6I / 6 copolymer, nylon 6T / 6I copolymer, nylon 6T / 6I / 66 copolymer, nylon 6T / M5-T copolymers are more preferred.

  In the resin composition of the present invention, the content of the resin (B1) is not particularly limited, but the lower limit thereof is preferably 1% by volume or more, more preferably 3% by volume or more with respect to the entire resin composition. 5% by volume or more is more preferable, 10% by volume or more is particularly preferable, and 14% by volume or more is most preferable. When the content of the resin (B1) is less than the lower limit, thermal conductivity, impact resistance, rigidity, heat resistance, and insulation tend to be difficult to improve sufficiently. The upper limit of the content of the resin (B1) is not particularly limited as long as the dispersed phase resin particles are formed by the resin (B1), but is preferably 90% by volume or less, more preferably 80% by volume or less. Preferably, it is more preferably 70% by volume or less, particularly preferably 60% by volume or less, and most preferably 50% by volume or less. When the content of the resin (B1) exceeds the upper limit, the dispersed phase resin particles due to the resin (B1) are difficult to be formed, and the insulating property tends to be lowered. , Impact resistance, rigidity and heat resistance tend to decrease.

  In the resin composition of the present invention, the lower limit of the content of the other resin (B2) is not particularly limited, but is preferably 10% by volume or more, more preferably 20% by volume or more with respect to the entire resin composition. Preferably, 30% by volume or more is more preferable, 40% by volume or more is particularly preferable, and 50% by volume or more is most preferable. Further, the upper limit of the content of the other resin (B2) is preferably 98% by volume or less, more preferably 96% by volume or less, still more preferably 94% by volume or less, particularly preferably 90% by volume or less, and 85% by volume. % Or less is most preferable. When the content of the other resin (B2) is less than the lower limit, a continuous phase due to the other resin (B2) is less likely to be formed, and the insulating property tends to decrease. The conductivity tends to decrease.

  In the present invention, when the volume of the resin (B1) is less than or equal to the volume of the other resin (B2), the resin (B1) stably forms dispersed phase resin particles, and the other resin (B2). ) Stably forms a continuous phase. Moreover, even when the capacity of the resin (B1) is larger than the capacity of the other resin (B2), the resin (B1) can be obtained by using a resin having a higher melt viscosity than the other resin (B2). B1) can stably form dispersed phase resin particles, and the other resin (B2) can stably form a continuous phase. In the present invention, the melt viscosity ratio of the resin (B1) and the other resin (B2) at the molding processing temperature is not particularly limited. For example, the resin (B1) and the other resin (B2) When the capacity ratio (V (B1) / V (B2)) is 1 or more, the resin (B1) and the other resins (from the viewpoint of stably forming dispersed phase resin particles) The ratio (η (B1) / η (B2)) of the melt viscosity at the molding processing temperature of B2) is preferably 1 or more, and more preferably 1.5 or more. For example, when the ratio (V (B1) / V (B2)) of the resin (B1) and the other resin (B2) is 3, the resin (B1) is stably dispersed phase resin particles. In order to form the ratio of the melt viscosity at the molding temperature of the resin (B1) and the other resin (B2) (η (B1) / η (B2)) is preferably 3 or more, More preferably, it is 4 or more. Furthermore, for example, when the volume ratio (V (B1) / V (B2)) of the resin (B1) and the other resin (B2) is 4, the resin (B1) is stably dispersed phase resin particles. In order to form the ratio of the melt viscosity at the molding temperature of the resin (B1) and the other resin (B2) (η (B1) / η (B2)) is preferably 4 or more, More preferably, it is 5 or more.

(C) Compound having functional group The compound having a functional group used in the present invention (hereinafter referred to as “functional group-containing compound (C)”) is the resin (B1) and the other resin (B2) of the present invention. Among them, those having reactivity with the resin (B1) and the other resin (B2) are preferable. The functional group-containing compound (C) of the present invention is extremely high in terminal groups such as amino groups, carboxyl groups, and hydroxyl groups of the resin (B) (that is, the resin (B1) and / or the other resin (B2)). Since it has reactivity, the reaction proceeds quickly. By using such a functional group-containing compound (C), the adhesion at the interface between the dispersed phase resin particles formed from the resin (B1) and the continuous phase formed from the other resin (B2) is improved. And the particle diameter of the dispersed phase resin particle which consists of said resin (B1) becomes small, and the connection structure concerning this invention is formed. In the present invention, when the functional group-containing compound (C) is reacted with the resin (B) (that is, the resin (B1) and / or the other resin (B2)), The reaction product is also included in the functional group-containing compound (C) according to the present invention.

  In the resin composition of the present invention, it is preferable that at least a part of the functional group-containing compound (C) (including the reaction product thereof) is present at the interface between the dispersed phase resin particles and the continuous phase. . As a result, the dispersed phase resin particles formed of the resin (B1) are reduced in diameter, and the connection structure according to the present invention can be formed. Further, the thermal resistance of the interface is reduced, the thermal conductivity of the resin composition is improved, and the insulating property of the interface tends to be improved.

  As such a functional group-containing compound (C), from the viewpoint of high affinity and / or reactivity with the resin (B1) and the other resin (B2), an alkoxysilyl group, a silanol group, and an epoxy group. A compound having at least one functional group selected from the group consisting of an isocyanate group, an amino group, a hydroxyl group, a mercapto group, a ureido group, a carboxyl group, a carboxylic anhydride group, an oxetane group and an oxazoline group is preferred.

  Specific examples of such a functional group-containing compound (C) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Such as epoxy group-containing alkoxysilane compounds; N-diglycidyl-N, N-bis (3- (methyldimethoxysilyl) propyl) amine, N-diglycidyl-N, N-bis (3- (trimethoxysilyl) propyl) amine, etc. An amine compound containing an epoxy group and an alkoxysilyl group; an isocyanate group-containing alkoxysilane such as 3- (trimethoxysilyl) propyl isocyanate and 3- (triethoxysilyl) propyl isocyanate; 1,3,5-N-tris ( 3-triethoxysilylpropyl) Isocyanurate group-containing alkoxysilanes such as socyanurate, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate; 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- ( N-phenyl) aminopropyltriethoxysilane Amino group-containing alkoxysilane compounds; alkoxysilyl group-containing vinyl compounds such as vinyltriethoxysilane; N, N-bis (3- (trimethoxysilyl) propyl) amine, N, N-bis (3- (trimethoxysilyl) Propyl) ethylenediamine, N, N-bis ((methyldimethoxysilyl) propyl) amine, N, N-bis (3- (methyldimethoxylyl) propyl) ethylenediamine and other amine compounds containing a plurality of alkoxysilyl groups; N, N -Alkoxysilyl such as bis (3- (trimethoxysilyl) propyl) methacrylamide, N, N-bis (3- (trimethoxysilyl) propyl) acrylamide, N, N-bis ((methyldimethoxysilyl) propyl) methacrylamide Group-containing amide compound; bis (3 Alkoxysilyl group-containing polysulfanes such as -triethoxysilylpropyl) polysulfane and bis (triethoxysilylethyltolylene) polysulfane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio Mercapto group-containing alkoxysilane compounds such as -1-propyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (2-ureidoethyl) ) Modified organosilane compounds such as ureido group-containing alkoxysilanes such as aminopropyltrimethoxysilane and 3- (2-ureidoethyl) aminopropyltriethoxysilane; Halosilane such as lanthanum and bromosilane and polyhalosilane; bisphenol A type epoxy compound such as bisphenol A-diglycidyl ether; bisphenol F type epoxy compound such as bisphenol F-diglycidyl ether; bisphenol AD type epoxy compound such as bisphenol AD-diglycidyl ether; glycidyl phthalate Examples thereof include glycidyl ester epoxy compounds such as esters; glycidyl amine epoxy compounds such as N-glycidyl aniline; novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins.

  Such a functional group containing compound (C) may be used individually by 1 type, or may use 2 or more types together. In the present invention, the interface between the dispersed phase resin particles and the continuous phase is strengthened, the amount of the connected structure formed from the anisotropic nanofiller (A) and the dispersed phase resin particles is increased, and the impact resistance and From the viewpoint of improving rigidity, the functional group-containing compound (C) is more preferably the modified organosilane compound, and among the modified organic silane compounds, an epoxy group-containing alkoxysilane compound, an epoxy group and an alkoxysilyl group. An amine compound containing an isocyanate group, an isocyanate group-containing alkoxysilane, an isocyanurate group-containing alkoxysilane, and an amino group-containing alkoxysilane compound are particularly preferred. The modified organosilane compound has extremely high reactivity with terminal groups such as amino group, carboxyl group and hydroxyl group of the resin (B), and in addition to the rapid progress of the reaction, the modified organosilane compounds Since polysiloxane is also formed by the polycondensation, an interface with extremely high adhesion can be formed between the dispersed phase resin particles and the continuous phase.

  In the resin composition of the present invention, the content of the functional group-containing compound (C) is not particularly limited, but is preferably 0.01% by volume or more, more preferably 0.05% by volume or more with respect to the entire resin composition. Preferably, 0.1% by volume or more is more preferable, 0.2% by volume or more is particularly preferable, 60% by volume or less is preferable, 50% by volume or less is more preferable, 40% by volume or less is further preferable, and 20% by volume. The following are particularly preferred: When the content of the functional group-containing compound (C) is less than the lower limit, the connection structure according to the present invention tends to be difficult to form, and the impact resistance tends to decrease. When it exceeds, it exists in the tendency for the moldability of a resin composition to fall.

(Filler)
In the resin composition of this invention, you may contain a filler as needed. Thereby, the intensity | strength of the resin composition obtained, rigidity, heat resistance, heat conductivity, etc. can be improved. Such a filler may be fibrous or non-fibrous such as granular. Specific examples thereof include glass fibers, carbon fibers, metal fibers, aramid fibers, cellulose fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, clay minerals represented by montmorillonite, mica (mica) ) Layered silicates represented by minerals and kaolin minerals, silica, calcium carbonate, magnesium carbonate, silicon oxide, calcium oxide, zirconium oxide, calcium sulfate, barium sulfate, titanium oxide, aluminum oxide and dolomite. The content of the filler in the resin composition of the present invention varies depending on the type of filler, and thus cannot be specified unconditionally. For example, it is preferably 0.05% by volume or more with respect to the entire resin composition, 0.1% More preferably, it is more preferably 1% by volume or more, more preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 70% by volume or less, and particularly preferably 60% by volume or less.

  Moreover, the resin composition of this invention can also be made to contain a heat conductive filler as a filler. Such a thermally conductive filler is not particularly limited, and examples thereof include alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, crystalline silica, fused silica, diamond, and zinc oxide. There is no restriction | limiting in particular as these shapes, For example, granular, flat form, rod shape, fiber shape, tube shape etc. are mentioned. These thermally conductive fillers may be used alone or in combination of two or more. The thermal conductivity of the thermally conductive filler is not particularly limited, but is preferably 0.5 W / (m · K) or more, more preferably 1 W / (m · K) or more, and 5 W / (m · K) or more. Is more preferably 10 W / (m · K) or more, and most preferably 20 W / (m · K) or more.

  The content of the heat conductive filler in the resin composition of the present invention is not particularly limited, but it is preferably 0.1% by volume or more, preferably 90% by volume or less, and 80% by volume or less with respect to the entire resin composition. Is more preferably 70% by volume or less, particularly preferably 50% by volume or less, and most preferably 40% by volume or less. If the content of the thermally conductive filler is less than the lower limit, the thermal conductivity of the resulting molded product tends not to be sufficiently improved. On the other hand, if the upper limit is exceeded, the specific gravity of the resin composition increases and the fluidity decreases. It tends to be easy to do.

(Other additives)
In the resin composition of the present invention, other components, for example, metal salt stabilizers such as copper chloride, cuprous iodide, copper acetate, cerium stearate, hindered amines, hindered phenols, sulfur-containing compounds, Antioxidants such as acrylate and phosphorus organic compounds, heat stabilizers, UV absorbers and weathering agents such as benzophenone, salicylate, and benzotriazole, light stabilizers, mold release agents, lubricants, crystal nucleating agents, viscosity Surface treatment agents such as regulators, colorants, silane coupling agents, pigments, fluorescent pigments, dyes, fluorescent dyes, anti-coloring agents, plasticizers, flame retardants (red phosphorus, metal hydroxide flame retardants, phosphorous flame retardants) Flame retardants, silicone flame retardants, halogen flame retardants, and combinations of these halogen flame retardants with antimony trioxide), wood powder, rice bran powder, walnut powder, waste paper, phosphorescent pigment, borate glass Antibacterial agents and antifungal agents such as, silver-based antimicrobial agent, magnesium - may be added to a mold corrosion inhibitor such as hydrotalcite represented by aluminum hydroxy hydrate.

<Resin composition and production method thereof>
Next, the manufacturing method of the resin composition of this invention is demonstrated. Examples of the method for producing the resin composition of the present invention include an anisotropic nanofiller (A), the resin (B1) that forms dispersed phase resin particles, the other resin (B2), and a functional group-containing compound (C ), And if necessary, a filler and other additives are mixed, and then mixed by melt kneading using a melt kneader such as an extruder; mixed by melt kneading using a Banbury mixer or rubber roll machine Methods and the like. The melt kneading apparatus is not particularly limited as long as it has sufficient kneading ability, and examples thereof include a uniaxial or multiaxial apparatus. The shape of each component is not particularly limited, and any shape such as pellets, powders, and strips may be used.

  In the method for producing a resin composition of the present invention, specific components may be mixed in advance, and the remaining components may be mixed. There is no particular limitation on the order and method of mixing, but the connecting structure according to the present invention. From the viewpoint that the body is suitably formed and the resulting resin composition has thermal conductivity, impact resistance, rigidity, heat resistance and insulating properties, the anisotropic nanofiller (A) and the dispersed phase resin particles are formed. A method in which the resin (B1), the other resin (B2), and the functional group-containing compound (C) are mixed together is particularly preferable.

  After the anisotropic nanofiller (A) and the resin (B1) (and, if necessary, the functional group-containing compound (C)) are mixed in advance by melt kneading using an extruder or the like, the remaining components are mixed. In addition, it may be mixed by melt kneading or the like, or the anisotropic nanofiller (A) and the resin (B1) (and optionally a functional group-containing compound (C)) may be added in advance to one or more It may be melt-kneaded by charging from the hopper upstream of the extruder equipped with a side feeder, and then each of the remaining components may be charged from one or more side feeders. Before mixing the other resin (B2), since the anisotropic nanofiller (A) is included in the resin (B1), the resin (B1) obtained after mixing the other resin (B2). Dispersed phase resin particles formed by The particle size is larger than that when the anisotropic nanofiller (A), the resin (B1) and the other resin (B2) are mixed together, and the content of the connection structure according to the present invention. Tend to decrease.

  The order of the filler and other additives is not particularly limited, but from the viewpoint of improving mechanical properties and thermal conductivity, the downstream of the inlet for charging the other resin (B2). It is preferable to add from the side feeder, and it is also preferable to add it separately using a single screw extruder or a twin screw extruder set in a screw arrangement with weak kneading ability.

In the production method of the present invention, a single anisotropic nanofiller (A) forms a connection structure in which two or more dispersed phase resin particles are present, thereby providing thermal conductivity, impact resistance, From the viewpoint of improving rigidity and heat resistance, it is necessary to perform melt kneading at a shear rate of 200 s ⁻¹ or more. In addition, from the viewpoint that the connection structure is easily formed and thermal conductivity, impact resistance, rigidity, and heat resistance are further improved, the shear rate during melt-kneading is preferably 300 s ⁻¹ or more, and 400 s ^−1. or more, and more preferably 500 s ^-1 or, particularly preferably 700 s ^-1 or higher, 1000 s ^-1 or more is most preferred. In addition, generally the shear rate in the case of melt-kneading a normal resin composition is 10-50 s- ¹ . In the production method of the present invention, the number average of dispersed phase resin particles formed of the resin (B1) is obtained by using the functional group-containing compound (C) by using the functional group-containing compound (C) by setting the shear rate to the above range. The particle diameter can be 2 μm or less, and furthermore, it is possible to form a connected structure in which a single anisotropic nanofiller (A) exists over two or more of the dispersed phase resin particles. .

In addition, the shear rate (unit: s ⁻¹ ) in melt kneading such as an extruder is represented by the following formula:
Shear rate (γ) = (π × D × N) / h
(In the formula, h represents the screw groove depth (unit: cm), D represents the screw diameter (unit: cm), and N represents the screw rotation speed (unit: rps)).
It can ask for.

In addition, in the case of an apparatus capable of measuring the shear stress τ and the viscosity μ, such as a precision same-direction biaxial kneader (“Microrheology Compounder HAAKE-MiniLab” manufactured by Thermo Fisher Scientific Co., Ltd.), the shear rate (Unit: s ⁻¹ ) is represented by the following formula:
Shear rate (γ) = τ / μ
It can ask for.

<Phase structure>
The resin composition of the present invention thus prepared includes the dispersed phase resin particles formed of the resin (B1) and the continuous phase formed of the other resin (B2) as described above. Is. In the resin composition of the present invention, the dispersed phase resin particles mean a portion where the resin (B1) is surrounded by the other resin (B2).

  The average particle diameter (number average value of diameter or major axis) of the dispersed phase resin particles is 2 μm or less, preferably 1 μm or less, more preferably 500 nm or less, still more preferably 400 nm or less, The thickness is particularly preferably 300 nm or less, and most preferably 200 nm or less. Further, the lower limit of the average particle diameter of the dispersed phase resin particles is preferably 0.3 nm or more, more preferably 0.4 nm or more, still more preferably 0.5 nm or more, and particularly preferably 1 nm or more. When the average particle diameter of the dispersed phase resin particles is in the above range, a resin composition excellent in impact resistance, rigidity and heat resistance can be obtained. On the other hand, when the average particle diameter of the dispersed phase resin particles exceeds the upper limit, the anisotropic nanofiller (A) tends to be included in the dispersed phase resin particles, and the connection structure according to the present invention is formed. It tends to be difficult. The average particle size of the dispersed phase resin particles can be reduced by increasing the shear rate during melt kneading or increasing the amount of the functional group-containing compound (C).

  In addition, the resin composition of the present invention includes a connected structure (in particular, the anisotropic nanofiller (A) in which a single anisotropic nanofiller (A) is present over two or more dispersed phase resin particles. In the case where A) has a one-dimensional structure, it contains a skewer structure. Furthermore, in the resin composition of the present invention, the ratio (number basis) of the anisotropic nanofiller (A) forming the connection structure to the total anisotropic nanofiller (A) is 10% or more ( It is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, particularly preferably 50% or more, and most preferably 60% or more. By containing the connection structure according to the present invention in such a ratio, the thermal conductivity, impact resistance, rigidity, heat resistance and insulation of the resin composition are improved.

Although there is no restriction | limiting in particular as the heat conductivity of the resin composition of this invention containing such a connection structure, 0.3 W / (m * K) or more is preferable, 0.4 W / (m * K) or more Is more preferable, 0.5 W / (m · K) or more is particularly preferable, and 0.6 W / (m · K) or more is most preferable. The volume resistivity is not particularly limited, but is preferably 10 ¹³ Ω · cm or more, more preferably 10 ¹⁴ Ω · cm or more, particularly preferably 10 ¹⁵ Ω · cm or more, and most preferably 10 ¹⁶ Ω · cm or more. preferable.

  The thermal conductivity is a value measured by the following method. That is, after the pellet-shaped resin composition is vacuum-dried under predetermined conditions (for example, conditions shown in Table 1), press molding is performed under predetermined molding conditions (for example, conditions shown in Table 1), and molding with a thickness of 2 mm is performed. Make a product. A 25 mm × 25 mm × 2 mm sample was cut out from this molded product, and was used at 40 ° C. (upper / lower temperature difference of 24 ° C.) using a steady-state thermal conductivity measuring device (for example, “GH-1” manufactured by ULVAC-RIKO Co., Ltd.). The thermal conductivity (W / mK) in the thickness direction of the sample is measured. The volume resistivity is a value measured by the following method. That is, after the pellet-shaped resin composition is vacuum-dried under predetermined conditions (for example, conditions shown in Table 1), press molding is performed under predetermined molding conditions (for example, conditions shown in Table 1), and molding with a thickness of 2 mm is performed. Make a product. A disk-shaped sample having a diameter of 100 mm and a thickness of 2 mm was cut out from the molded product, and a high resistance meter (for example, “AGILENT 4339B” manufactured by Agilent Technologies, Inc.) was used, and 100 V was applied in accordance with JIS K6911. The subsequent volume resistivity is measured.

  FIG. 1 schematically shows the phase structure of such a resin composition, but the phase structure of the resin composition of the present invention is not limited to this. The dispersed phase resin particles 2 are formed of the resin (B1). In this case, as long as the dispersed phase resin particles 2 and the continuous phase 3 are formed, the other resin (B2) other than the other resin having affinity with the anisotropic nanofiller (A) 1 and the resin (B1). ) May be contained in the dispersed phase resin particles 2. The shape of the dispersed phase resin particles 2 is not particularly limited, and may be a perfect circle or a non-circular shape such as a stripe shape, a polygonal shape, or an elliptical shape.

The continuous phase 3 is formed of the other resin (B2), but the resin (B1) may be included as long as the dispersed phase resin particles 2 and the continuous phase 3 are formed. The continuous phase 3 may contain an anisotropic nanofiller (A). However, in applications where insulation is required, the content of the continuous phase 3 is the insulation (volume resistivity of the resin composition). Preferably, it is in a range where 10 ¹³ Ω · cm or more is maintained.

  In the resin composition of the present invention, it is preferable that at least a part (more preferably all) of the functional group-containing compound (C) is present at the interface 4 between the dispersed phase resin particles 2 and the continuous phase 3. Thus, when the functional group-containing compound (C) is present at the interface 4 between the dispersed phase resin particles 2 and the continuous phase 3, the dispersed phase resin particles 2 tend to be reduced in diameter.

  In the case where a resin having a reactive functional group such as a terminal reactive group is used as at least one of the two or more types of resins (B), from the viewpoint of improving thermal conductivity, the functional group At least a part (preferably all) of the functional groups of the containing compound (C) is bonded to the reactive functional group in the resin (B1) and / or the other resin (B2) by a chemical reaction. preferable. Thereby, a stable layer is formed at the interface 4 between the dispersed phase resin particles 2 and the continuous phase 3, and a large number of connected structures according to the present invention can be formed.

  In addition, at the interface 4 between the dispersed phase resin particles 2 and the continuous phase 3, it is more preferable that the functional group-containing compound (C) and / or the reaction product thereof react with each other. Thereby, the layer formed at the interface 4 between the dispersed phase resin particles 2 and the continuous phase 3 becomes thicker and stronger, the insulation is further improved, and the thermal resistance of the interface is further reduced (the thermal conductivity is further increased). Improved) and impact resistance tends to be improved.

  For example, when polyarylene sulfide is used as the dispersed phase resin particles and polyamide is used as the continuous phase, the SNa group that is the terminal group of the polyarylene sulfide, the SH group generated by acid treatment from the SNa group, and the like An amino group which is an amino group, a carboxyl group, an acid anhydride group, an epoxy group, or an end group formed by reaction of N-methylpyrrolidone used during the production or an end group of polyamide The carboxyl group, the amide group of the main chain and the like react with the functional group of the functional group-containing compound (C) during mixing such as melt kneading to form a stable interface layer. As a result, a connected structure in which the anisotropic nanofiller (A) exists over two or more dispersed phase resin particles formed of polyarylene sulfide is formed.

  Also, for example, in the case where polyarylene sulfide is used as the dispersed phase resin particles and the polyester resin is used as the continuous phase, the SNa group that is the terminal group of the polyarylene sulfide, the SH group generated by acid treatment or the like from the SNa group, Amino group, carboxyl group, acid anhydride group, epoxy group introduced at the time of production or after treatment as required, or terminal group formed by reaction of N-methylpyrrolidone used at the time of production, and polyester-based resin The terminal hydroxyl group, carboxyl group, main chain ester group and the like react with the functional group of the functional group-containing compound (C) during mixing such as melt-kneading to form a stable interface layer. As a result, a connected structure in which the anisotropic nanofiller (A) exists over two or more dispersed phase resin particles formed of polyarylene sulfide is formed.

  Furthermore, for example, in the case of using a polyamide as the dispersed phase resin particles and a polyester resin as the continuous phase, the amino group which is the terminal group of the polyamide, the amide group of the carboxyl group or the main chain, and the terminal group of the polyester resin. Hydroxyl groups, carboxyl groups, main chain ester groups and the like react with the functional groups of the functional group-containing compound (C) during mixing such as melt kneading to form a stable interface layer. As a result, a connected structure in which the anisotropic nanofiller (A) exists over two or more dispersed phase resin particles formed of polyamide is formed.

  In the interface layer, a crosslinking reaction such as a reaction between the alkoxysilyl group and silanol group of the functional group-containing compound (C) and / or its reaction product (polysiloxane structure formation reaction), an epoxy group reaction, etc. occurs. In addition, the interface layer becomes thicker and stronger, and the dispersed phase resin particles made of the resin (B1) are reduced in diameter, so that impact resistance, rigidity, and heat resistance are improved.

  The phase structure of such a resin composition can be confirmed by observing with a scanning electron microscope or a transmission electron microscope. In particular, when a reaction product is formed at the interface by the reaction between the functional group-containing compound (C) and the resin (B1) and / or the other resin (B2), the reaction product is formed. The interface layer can be confirmed by observation using a transmission electron microscope or a scanning force microscope (for example, elastic modulus mode).

  Further, in the resin composition of the present invention, the functional group-containing compound (C) present at the interface between the dispersed phase resin particles and the continuous phase with respect to the total functional group-containing compound (C) (the resin (B1) and / or the other The ratio W of the resin (including those reacted with the resin (B2)) is not particularly limited, but is preferably 20% by volume or more, more preferably 50% by volume or more, still more preferably 60% by volume or more, and 80% by volume. % Or more is particularly preferable, and 100% by volume is most preferable. When the ratio W is less than the lower limit, the insulation properties are lowered, and the impact resistance and rigidity tend to be lowered.

  In the present invention, the value of W can be obtained based on a transmission electron micrograph as follows. That is, an arbitrary portion of the ultrathin slice at the central central portion of the molded article made of the resin composition is observed using a transmission electron microscope (TEM). In the obtained TEM photograph, four parts are randomly extracted within the range of 4.5 μm × 4.5 μm in terms of the size of the molded product. The mass of the extracted range is measured, the portion where the functional group-containing compound (C) is present is cut out from the extracted range, the mass of the photograph of the cut-out portion is measured, and the mass ratio (mass of the photo relating to the predetermined portion) %). Among these, the mass of the photograph of the part applicable to the functional group containing compound (C) which exists in the interface of a dispersed phase resin particle and a continuous phase is also measured, and it is continuous with the dispersed phase resin particle with respect to all the functional group containing compounds (C). The ratio W of the functional group-containing compound (C) present at the interface with the phase (including those reacting with the resin (B1) and / or the other resin (B2)) is determined. Here, since the thickness of the used printing paper is uniform, it can be regarded as an actual capacity ratio (capacity%) regarding a predetermined portion. This capacity ratio is obtained for any of the four extracted locations, and the average value is defined as W (volume%).

  In the resin composition of the present invention, when at least a part of the functional group-containing compound (C) is present at the interface between the dispersed phase resin particles and the continuous phase, the functional group-containing compound (C) and the resin (B1). The thickness of the reaction product with the other resin (B2) is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, particularly preferably 20 nm or more, and 50 nm or more. Is most preferred. When the thickness of the reaction product is less than the lower limit, the insulating property is lowered and the anisotropy of thermal conductivity tends to increase.

  In the present invention, it is preferable that at least one end of the anisotropic nanofiller (A) forming the connection structure is present in the dispersed phase resin particles, and both ends are present in the dispersed phase resin particles. It is particularly preferred. By the formation of the connection structure according to the present invention, re-aggregation due to van der Waals force between anisotropic nanofillers (A) during melt-kneading or molding is inhibited by the presence of a plurality of dispersed phase resin particles. The formation of an electric conduction path by the anisotropic nanofiller (A) can be suppressed, and a decrease in insulation can be prevented. However, at least one end of the anisotropic nanofiller (A), preferably both ends are When it exists in the dispersed phase resin particle which consists of resin (B1), formation of an electric conduction path can be prevented more suitably and insulation is improved. Further, when the anisotropic nanofiller (A) has at least one end, preferably both ends, in the dispersed phase resin particles made of the resin (B1), the anisotropic nanofiller (A) is also anisotropic when an external force is applied. Since it becomes more difficult to pull out the nanofiller (A) from the resin, the impact resistance is improved.

  Although there is no restriction | limiting in particular as a method of processing such a resin composition of this invention into a molded object, A melt molding process is preferable. Examples of such melt molding methods include conventionally known molding methods such as injection molding, extrusion molding, blow molding, press molding, compression molding, and gas assist molding. In addition, the orientation of the anisotropic nanofiller (A) or the resin (B) can be controlled by applying a magnetic field, an electric field, an ultrasonic wave, or the like during the molding process.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the physical property etc. of the obtained resin composition were measured with the following method.

(1) Shear rate The shear rate at the time of melt kneading in the case of using a precision same-direction biaxial kneader ("Microrheology Compounder HAAKE-MiniLab" manufactured by Thermo Fisher Scientific Co., Ltd.) is determined as follows. It was. That is, the shear stress τ and the viscosity μ were measured 5 minutes after the start of melt kneading using the kneader. Using this shear stress τ and viscosity μ, the shear rate (unit: s ⁻¹ ) was determined by the following formula.
Shear rate (γ) = τ / μ
Further, the shear rate (unit: s ⁻¹ ) at the time of melt kneading when using a biaxial melt kneading extruder (manufactured by Technobel, screw diameter: 15 mm, L / D: 60) was determined by the following equation .
Shear rate (γ) = (π × D × N) / h
In the above formula, h represents the screw groove depth (unit: cm), D represents the screw diameter (unit: cm), and N represents the screw rotation speed (unit: rps). In the following examples and comparative examples, h was 0.25 cm.

(2) Observation with Transmission Electron Microscope (TEM) The pellet-shaped resin composition was vacuum dried under the conditions shown in Table 1 and then press-molded at the temperatures shown in Table 1 to obtain a molded product having a thickness of 2 mm. A sample having a length of 40 mm, a width of 5 mm, and a thickness of 2 mm was cut out from the molded article, and an arbitrary portion of the ultrathin slice at the center of the sample was observed using a transmission electron microscope (TEM).

(3) Average particle diameter of dispersed phase resin particles In the TEM photograph obtained in (2) above, a range of 18 μm × 18 μm was randomly extracted in the size of the molded product. The particle diameter of the dispersed phase resin particles observed in the extracted range of one place was measured, and the number average value was obtained as the average particle diameter of the dispersed phase resin particles.

(4) Ratio of anisotropic nanofiller (A) forming a connected structure In the TEM photograph obtained in (2) above, the size of the molded product is not in the range of 4.5 μm × 4.5 μm. Four points were extracted for the purpose. The number of the total anisotropic nanofillers (A) observed in the four extracted ranges and the anisotropic nanofillers (A) present in the two or more dispersed phase resin particles. The number was determined, and the ratio (number basis, unit:%) of the anisotropic nanofiller (A) forming the connected structure to the total anisotropic nanofiller (A) was determined.

(5) Thermal conductivity After the pellet-shaped resin composition was vacuum-dried under the conditions shown in Table 1, press molding was performed at the temperature shown in Table 1 to obtain a molded product having a thickness of 2 mm. A sample having a length of 25 mm, a width of 25 mm, and a thickness of 2 mm was cut out from the molded product, and the temperature was measured at 40 ° C. using a steady-state thermal conductivity measuring device (“GH-1” manufactured by ULVAC-RIKO Co., Ltd.). ), The thermal conductivity (unit: W / (mK)) in the thickness direction of the sample was measured.

(6) Charpy impact strength After the pellet-shaped resin composition was vacuum-dried under the conditions shown in Table 1, injection molding was performed at the temperature shown in Table 1 to obtain a molded product of length 80 mm x width 10 mm x thickness 4 mm. . A notch (V type, notch angle: 45 °, notch depth: 2 mm) is produced on this molded product using a notching tool (“A-3 type” manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a notched specimen is prepared. Obtained. About this test piece, the Charpy impact strength (unit: kJ / m ² ) with a notch was measured at 23 ° C. according to ISO179 using a Charpy impact tester (“DG-UB” manufactured by Toyo Seiki Seisakusho Co., Ltd.). The average value (N = 5) was obtained.

(7) Flexural modulus After the pellet-shaped resin composition was vacuum dried under the conditions shown in Table 1, injection molding was performed at the temperature shown in Table 1 to obtain a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. . About this test piece, the bending elastic modulus (unit: GPa) was measured at 23 ° C. according to ISO178 using an autograph (“AGS-10kNG” manufactured by Shimadzu Corporation), and the average value (N = 5) )

(8) Storage elastic modulus at high temperature After the pellet-shaped resin composition was vacuum-dried under the conditions shown in Table 1, press molding was performed at the temperature shown in Table 1 to obtain a molded product having a thickness of 1 mm. A sample having a length of 40 mm, a width of 4 mm, and a thickness of 1 mm was cut out from the molded product, and a temperature range: −150 ° C. using a dynamic viscoelasticity measuring device (“itk DVA-220” manufactured by IT Measurement Control Co., Ltd.). ˜200 ° C., heating rate: 5 ° C./min, deformation mode: tensile, strain: 0.05%, measurement frequency: 10 Hz, distance between chucks: 25 mm The elastic modulus (unit: GPa) was determined.

(9) Volume resistivity After pellet-shaped resin composition was vacuum-dried on the conditions shown in Table 1, press molding was performed at the temperature shown in Table 1, and the molded article of thickness 2mm was obtained. A disk-shaped sample having a diameter of 100 mm and a thickness of 2 mm was cut out from the molded product, and 100 V was applied in accordance with JIS K6911 using a high resistance meter (“AGILENT 4339B” manufactured by Agilent Technologies, Inc.) 1 minute later. Volume resistivity was measured.

Moreover, the anisotropic nanofiller (A), resin (B), and functional group containing compound (C) which were used in the Example and the comparative example are shown below. In addition, the G / D value of the following anisotropic nanofiller (A) was measured at an excitation laser wavelength of 532 nm using a laser Raman spectroscopy system [“NRS-3300” manufactured by JASCO Corporation], and was about 1585 cm ^{−. It} was determined from the peak intensities of the Raman spectrum of the G band observed in the vicinity of ¹ and the D band observed in the vicinity of about 1350 cm ⁻¹ .

(A) Anisotropic nanofiller:
Anisotropic nanofiller (a-1)
Multi-walled carbon nanotube (“NT-7” manufactured by Hodogaya Chemical Co., Ltd., diameter distribution 40 to 90 nm, aspect ratio 100 or more, G / D value 8.0).

(B1) Resin forming dispersed phase resin particles:
・ Resin (b1-1)
Polyphenylene sulfide (“Fortron W202A” manufactured by Kureha Corporation, linear polyphenylene sulfide having a melt viscosity of 20 Pa · s at a temperature of 310 ° C. and a shear rate of 1200 sec− ¹ , specific gravity of 1.35). In addition, resin (b1-1) is resin with high affinity with anisotropic nanofiller (a-1) compared with the following resin (b2-1).

(B2) Resin that forms a continuous phase:
・ Resin (b2-1)
Polyamide (Nylon 6 “1022B” manufactured by Ube Industries, Ltd.).

(C) Functional group-containing compound:
-Functional group-containing compound (c-1)
3-glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.).

(D) Modified polyolefin polymer / modified polyolefin polymer (d-1)
Epoxy-modified polyethylene (“Bond First-E” manufactured by Sumitomo Chemical Co., Ltd., glycidyl methacrylate content 12 mass%, specific gravity 0.94).

Example 1
1% by volume of anisotropic nanofiller (a-1), 21% by volume of resin (b1-1), 77.5% by volume of resin (b2-1), and functional group with respect to a total of 100% by volume of all components 0.5% by volume of the compound (c-1) contained, and charged into a precision same-direction biaxial kneader (“Microrheology Compounder HAAKE-MiniLab” manufactured by Thermo Fisher Scientific Co., Ltd.), nitrogen atmosphere The melt kneading was carried out for 5 minutes while circulating the molten resin in the kneader under the conditions of a temperature of 290 ° C. and a screw rotation speed of 200 rpm. The kneader is capable of imparting high shear in the route during circulation of the molten resin, and can observe the shear rate during circulation. The shear rate during the melt kneading for 5 minutes was 714 s ⁻¹ . The discharged kneaded material was extruded into a strand shape, cooled, and then cut with a strand cutter to obtain a pellet-shaped resin composition. When this resin composition was observed using a transmission electron microscope (TEM), dispersed phase resin particles were formed by the resin (b1-1), and a continuous phase was formed by the resin (b2-1). It was confirmed that a connected structure (skew-like structure) in which one anisotropic nanofiller (a-1) is present over two or more dispersed phase resin particles is formed (FIG. 2). . Moreover, about this resin composition, the average particle diameter of the dispersed phase resin particles forming the connection structure, the ratio of the anisotropic nanofiller (A) forming the connection structure, the thermal conductivity, and the Charpy impact Strength, flexural modulus, storage modulus at high temperature, and volume resistivity were measured according to the methods described above. The results are shown in Table 2.

(Example 2)
Melt kneading was carried out for 5 minutes in the same manner as in Example 1 except that the screw rotation speed was changed to 300 rpm. The shear rate during the melt kneading for 5 minutes was 1070 s ⁻¹ . Thereafter, a pellet-shaped resin composition was produced in the same manner as in Example 1. When this resin composition was observed using a transmission electron microscope (TEM), it was confirmed that a connected structure (skew-like structure) was formed. Moreover, about this resin composition, the average particle diameter of the dispersed phase resin particles forming the connection structure, the ratio of the anisotropic nanofiller (A) forming the connection structure, the thermal conductivity, and the Charpy impact Strength, flexural modulus, storage modulus at high temperature, and volume resistivity were measured according to the methods described above. The results are shown in Table 2.

(Example 3)
A pellet-shaped resin composition in the same manner as in Example 1 except that the amount of the anisotropic nanofiller (a-1) was changed to 2% by volume and the amount of the resin (b2-1) was changed to 76.5% by volume. Was made. When this resin composition was observed using a transmission electron microscope (TEM), it was confirmed that a connected structure (skew-like structure) was formed. Moreover, about this resin composition, the average particle diameter of the dispersed phase resin particles forming the connection structure, the ratio of the anisotropic nanofiller (A) forming the connection structure, the thermal conductivity, and the Charpy impact Strength, flexural modulus, storage modulus at high temperature, and volume resistivity were measured according to the methods described above. The results are shown in Table 2.

Example 4
A pellet-shaped resin composition as in Example 1 except that the amount of the anisotropic nanofiller (a-1) was changed to 3% by volume and the amount of the resin (b2-1) was changed to 75.5% by volume. Was made. When this resin composition was observed using a transmission electron microscope (TEM), it was confirmed that a connected structure (skew-like structure) was formed. Moreover, about this resin composition, the average particle diameter of the dispersed phase resin particles forming the connection structure, the ratio of the anisotropic nanofiller (A) forming the connection structure, the thermal conductivity, and the Charpy impact Strength, flexural modulus, storage modulus at high temperature, and volume resistivity were measured according to the methods described above. The results are shown in Table 2.

(Example 5)
Melt-kneading was carried out for 5 minutes in the same manner as in Example 1 except that the screw rotation speed was changed to 100 rpm. The shear rate during the melt kneading for 5 minutes was 357 s ⁻¹ . Thereafter, a pellet-shaped resin composition was produced in the same manner as in Example 1. When this resin composition was observed using a transmission electron microscope (TEM), it was confirmed that a connected structure (skew-like structure) was formed. Moreover, about this resin composition, the average particle diameter of the dispersed phase resin particles forming the connection structure, the ratio of the anisotropic nanofiller (A) forming the connection structure, the thermal conductivity, and the Charpy impact Strength, flexural modulus, storage modulus at high temperature, and volume resistivity were measured according to the methods described above. The results are shown in Table 2.

(Comparative Example 1)
A pellet-shaped resin composition was prepared in the same manner as in Example 1 except that the functional group-containing compound (c-1) was not used and the amount of the resin (b2-1) was changed to 78.0% by volume. When this resin composition was observed using a transmission electron microscope (TEM), dispersed phase resin particles were formed by the resin (b1-1), and a continuous phase was formed by the resin (b2-1). A connection structure (skew-like structure) was not formed (FIG. 3). Further, with respect to this resin composition, the average particle diameter, thermal conductivity, Charpy impact strength, bending elastic modulus, storage elastic modulus at high temperature, and volume resistivity of the dispersed phase resin particles were measured according to the above methods. The results are shown in Table 2.

(Comparative Example 2)
1% by volume of anisotropic nanofiller (a-1), 21% by volume of resin (b1-1), 77.5% by volume of resin (b2-1), and functional group with respect to a total of 100% by volume of all components The compound (c-1) 0.5% by volume was blended and charged into a twin-screw melt-kneading extruder (manufactured by Technobel, screw diameter: 15 mm, L / D: 60), and a cylinder set temperature of 290 ° C. Then, melt kneading was performed under the condition of a screw rotation speed of 100 rpm. The shear rate during melt kneading was 31 s ⁻¹ . The discharged kneaded material was extruded into a strand shape, cooled, and then cut with a strand cutter to obtain a pellet-shaped resin composition. When this resin composition was observed using a transmission electron microscope (TEM), a connection structure (skew-like structure) was not formed. Further, with respect to this resin composition, the average particle diameter, thermal conductivity, Charpy impact strength, bending elastic modulus, storage elastic modulus at high temperature, and volume resistivity of the dispersed phase resin particles were measured according to the above methods. The results are shown in Table 2.

(Comparative Example 3)
A pellet-shaped resin composition was prepared in the same manner as in Comparative Example 2 except that the anisotropic nanofiller (a-1) was not used and the amount of the resin (b2-1) was changed to 78.5% by volume. . With respect to this resin composition, the average particle diameter, thermal conductivity, Charpy impact strength, bending elastic modulus, storage elastic modulus at high temperature, and volume resistivity of the dispersed phase resin particles were measured according to the above methods. The results are shown in Table 2.

(Comparative Example 4)
A pellet-shaped resin composition was prepared in the same manner as in Comparative Example 2 except that 0.5% by volume of the modified polyolefin polymer (d-1) was used instead of the functional group-containing compound (c-1). When this resin composition was observed using a transmission electron microscope (TEM), a connection structure (skew-like structure) was not formed. Further, with respect to this resin composition, the average particle diameter, thermal conductivity, Charpy impact strength, bending elastic modulus, storage elastic modulus at high temperature, and volume resistivity of the dispersed phase resin particles were measured according to the above methods. The results are shown in Table 2.

(Comparative Example 5)
A pellet-shaped resin composition was prepared in the same manner as in Example 1 except that 0.5 volume% of the modified polyolefin polymer (d-1) was used instead of the functional group-containing compound (c-1). When this resin composition was observed using a transmission electron microscope (TEM), a connection structure (skew-like structure) was not formed. Further, with respect to this resin composition, the average particle diameter, thermal conductivity, Charpy impact strength, bending elastic modulus, storage elastic modulus at high temperature, and volume resistivity of the dispersed phase resin particles were measured according to the above methods. The results are shown in Table 2.

As is apparent from the results shown in Table 2, the anisotropic nanofiller (A), the resin (B1), the resin (B2), and the functional group-containing compound (C) are subjected to a high shear rate of 200 s ⁻¹ or more. The resin compositions (Examples 1 to 5) of the present invention mixed in the dispersion phase are dispersed phases in which the average particle diameter of the dispersed phase resin particles is as small as 1 μm or less and the single anisotropic nanofiller (A) is 2 or more. It was confirmed that the content of the anisotropic nanofiller (A) forming the connection structure was as high as 45% or more, including the connection structure existing over the resin particles. Moreover, the resin composition containing such a connection structure has high thermal conductivity and insulating properties, and has high Charpy impact strength, rigidity (flexural modulus), and heat resistance (high temperature storage). It was confirmed that the elastic modulus was excellent.

  On the other hand, when the anisotropic nanofiller (A), the resin (B1), and the resin (B2) are mixed at a high shear rate without blending the functional group-containing compound (C) (Comparative Example 1). No connection structure was formed, and the obtained resin composition contained a dispersed phase having a very large particle size, and the average particle size was increased. Although such a resin composition was excellent in thermal conductivity, it was found that the resin composition was inferior in insulation and inferior in Charpy impact strength, rigidity (flexural modulus) and heat resistance (high temperature storage modulus).

Further, when the anisotropic nanofiller (A), the resin (B1), the resin (B2) and the functional group-containing compound (C) are mixed at a low shear rate of 100 s ⁻¹ or less (Comparative Example 2). No connection structure was formed, and dispersed phase resin particles having a large average particle diameter were formed. Such a resin composition was found to be inferior in Charpy impact strength, rigidity (bending elastic modulus) and heat resistance (high temperature storage elastic modulus), although having high thermal conductivity and insulating properties.

  Furthermore, when mixed at a low shear rate without blending the anisotropic nanofiller (A) (Comparative Example 3), the thermal conductivity is inferior compared to the resin composition of Comparative Example 2, and the rigidity ( Flexural modulus) was further reduced. In addition, when the modified polyolefin polymer (D) is used instead of the functional group-containing compound (C) and mixed at a low shear rate (Comparative Example 4), compared to the resin composition of Comparative Example 2, The average particle diameter of the dispersed phase resin particles further increased, and the Charpy impact strength and heat resistance (high temperature storage elastic modulus) further decreased.

  When the modified polyolefin polymer (D) is used instead of the functional group-containing compound (C) and mixed at a high shear rate (Comparative Example 5), compared to the resin composition of Example 1, The average particle size of the dispersed phase resin particles was increased. This is because the modified polyolefin polymer (D) is less reactive with the resin (B1) than the functional group-containing compound (C), and the dispersed phase resin particles formed by the resin (B1) are finer. It is guessed that it was not done. Further, in the resin composition of Comparative Example 5, no connection structure was formed. This is because the modified polyolefin polymer (D) has a very low affinity with the anisotropic nanofiller (A) compared to the functional group-containing compound (C), and the anisotropic nanofiller (A) is a resin. This is presumed to be confined to the dispersed phase formed by (B1). Such a resin composition was found to be inferior in thermal conductivity, Charpy impact strength, rigidity (flexural modulus) and heat resistance (high temperature storage modulus).

  As described above, according to the present invention, it is possible to obtain a resin composition having both high thermal conductivity and insulating properties and excellent in impact resistance, rigidity and heat resistance.

  Therefore, the resin composition of the present invention is used in applications requiring thermal conductivity, impact resistance, rigidity, heat resistance, insulation, etc., for example, various parts for automobiles, various parts for electrical and electronic equipment, and high thermal conductivity. It is useful for applications such as sheets, heat sinks, and electromagnetic wave absorbers.

1: Anisotropic nanofiller (A)
2: Dispersed phase resin particles 3: Continuous phase 4: Interface between dispersed phase resin particles and continuous phase (compound having functional group (C))

Claims (4)

Dispersed phase resin particles containing the anisotropic nanofiller (A) and two or more kinds of resins (B) and formed of one kind of the two or more kinds of resins (B) (B1) and the rest And a continuous phase formed from one or more resins (B2).
The dispersed phase resin particles have an average particle size (number average) of 2 μm or less,
A single anisotropic nanofiller (A) contains a connecting structure that exists over two or more dispersed phase resin particles,
The resin composition, wherein the ratio (number basis) of the anisotropic nanofiller (A) forming the connection structure to the total anisotropic nanofiller (A) is 10% or more. The resin (B1) is a resin (B _aff ) having the highest affinity with the anisotropic nanofiller (A) of the two or more types of resins (B). The resin composition as described.   The resin composition according to claim 1 or 2, further comprising a compound (C) having a functional group. Dispersed phase resin particles containing the anisotropic nanofiller (A) and two or more kinds of resins (B) and formed of one kind of the two or more kinds of resins (B) (B1) and the rest A process for producing a resin composition comprising a continuous phase formed of one or more kinds of resins (B2),
By mixing the anisotropic nanofiller (A), the resin (B1), the resin (B2) and the compound (C) having a functional group under a shear rate of 200 s ⁻¹ or more,
Forming the dispersed phase resin particles having an average particle diameter (number basis) of 2 μm or less,
A single anisotropic nanofiller (A) forms a connected structure in which two or more dispersed phase resin particles exist,
A method for producing a resin composition, comprising forming the connection structure on 10% or more (several standards) of the total anisotropic nanofiller (A).