JP6167011B2 - Electrically insulating high thermal conductive resin composition - Google Patents

Description

  The present invention relates to an electrically insulating high thermal conductive resin composition using a polyarylene sulfide resin.

Polyarylene sulfide resin (hereinafter sometimes referred to as “PAS resin”) represented by polyphenylene sulfide resin (hereinafter sometimes referred to as “PPS resin”) has high heat resistance, mechanical properties, chemical resistance, Since it has dimensional stability and flame retardancy, it is widely used in electrical and electronic equipment component materials, automotive equipment component materials, chemical equipment component materials, and the like. A highly thermally conductive resin composition in which a PAS resin and a thermally conductive filler are blended is known utilizing the heat resistance of such a PAS resin and the thermal conductivity of the thermally conductive filler. Examples of the thermally conductive filler include metal fillers made of metals such as copper, silver, iron, aluminum or alloys thereof, carbon fillers such as carbon and graphite, alumina, magnesium oxide, beryllium oxide, and zinc oxide. A filler made of a metal oxide such as titanium oxide is used.
Among these, magnesium oxide is useful because it has a relatively high thermal conductivity and appropriate hardness and insulation, and the present applicant consists of surface-treated magnesium oxide, that is, a magnesium phosphate compound. A highly thermally conductive resin composition containing magnesium oxide having a coating layer and the like, and a PAS resin has been proposed (Patent Document 1). This high heat conductive resin composition solved the problem of improving moldability and heat and humidity resistance.

In addition, as a resin composition using PAS resin and surface-treated magnesium oxide, the resin composition described in patent documents 2-4 is mentioned.
Patent Document 2 describes a resin composition containing a PAS resin and magnesium oxide surface-treated with an alkoxysilane compound. In this resin composition, the purpose of using the surface-treated magnesium oxide is to impart corrosion resistance. Moreover, the addition amount of the said magnesium oxide is a small amount, and is not the quantity which can exhibit high thermal conductivity by the resin composition. That is, the resin composition is not a resin composition having high thermal conductivity.
Patent Document 3 describes a resin composition (molding material for electrical insulation / heat radiation component) containing a PAS resin and magnesium oxide obtained by surface treatment after baking at 800 ° C. or higher. In this resin composition, the purpose of using the surface-treated magnesium oxide is to impart high thermal conductivity and wet heat resistance. And the feature of the said surface-treated magnesium oxide is in performing surface treatment after baking at 800 degreeC or more. Examples of the surface treatment agent used for the surface treatment include silane coupling agents and titanate coupling agents.
Patent Document 4 discloses a thermally conductive polymer composition (metal / polymer hybrid article) containing a thermoplastic polymer, magnesium oxide (coated with a coupling agent such as silane), and filler (glass fiber) in a predetermined ratio. Is described. This thermally conductive polymer composition is intended to improve thermal conductivity, mechanical strength, etc., but bending strength and thin wall fluidity are not considered.

In recent years, parts of various products such as electric products have been reduced in size and thickness, and a resin composition having excellent thin-wall fluidity while maintaining high thermal conductivity and excellent mechanical properties has been demanded.
Although the high thermal conductive resin composition described in Patent Document 1 exhibits high fluidity, it does not have fluidity that can be said to be excellent in thin-walled fluidity. The resin compositions described in other patent documents do not have thin-wall fluidity.

JP 2006-28283A JP-A-8-12886 JP 2002-38010 A Special table 2013-500352 gazette

  The present invention has been made in view of the above-described conventional technology, and the problem is that an electrically insulating thermally conductive resin composition having high bending strength while maintaining high thermal conductivity and excellent thin-wall fluidity. Is to provide.

The present invention for solving the above problems is as follows.
(1) An electrically insulating material comprising (A) a polyarylene sulfide resin, (B) magnesium oxide pre-treated with a vinylalkoxysilane compound, (C) glass fiber, and (D) an alkoxysilane compound. A highly thermally conductive resin composition comprising:
The total content of the component (B) and the component (C) is 80 to 130 parts by mass with respect to 100 parts by mass of the component (A), and the component (B) with respect to 100 parts by mass of the component (A). The total content (parts by mass) of the component and the component (C) is the x axis, and the content (mass%) of the component (B) relative to the total content of the component (B) and the component (C) is the y axis. , Point a represented by x = 83 (mass part), y = 88.9 (mass%), point represented by x = 101 (mass part), y = 80.0 (mass%) b, point c represented by x = 124 (mass part), y = 54.5 (mass%), point d represented by x = 101 (mass part), y = 90.0 (mass%), And a line segment ab, a line segment bc, and a line segment c, with five points consisting of a point e represented by x = 124 (parts by mass) and y = 72.7 (% by mass) as vertices. The content ratio of the component (B) with respect to the total content of the component (B) and the component (C) is present in the region of the figure composed of e, the line segment ed, and the line segment da. High thermal conductive resin composition.

(2) The high thermal conductive resin composition according to (1), wherein the (D) alkoxysilane compound is contained in an amount of 0.45 to 1.5 parts by mass with respect to 100 parts by mass of the component (A).

(3) Furthermore, (E) High thermal conductive resin as described in said (1) or (2) which has 5-15 mass parts of epoxy group containing olefin type copolymers with respect to 100 mass parts of said (A) component. Composition.

(4) The above (1) to (3), wherein the component (E) is an olefin copolymer comprising a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. ). The high thermal conductive resin composition according to any one of the above.

(5) The high thermal conductive resin composition according to (4), wherein the component (E) is an olefin copolymer further containing a structural unit derived from a (meth) acrylic acid ester.

  According to the present invention, it is possible to provide an electrically insulating thermally conductive resin composition having high bending strength while maintaining high thermal conductivity and excellent thin-wall fluidity.

It is a figure which shows the relationship of the content rate of (B) surface treatment magnesium oxide with respect to the total content of (B) surface treatment magnesium oxide and (C) glass fiber.

The highly thermally conductive resin composition of the present invention comprises (A) a polyarylene sulfide resin, (B) magnesium oxide pre-treated with a vinylalkoxysilane compound, (C) glass fiber, and (D) an alkoxysilane compound. And an electrically insulating high thermal conductive resin composition comprising a total content of the component (B) and the component (C) of 80 to 130 parts by mass with respect to 100 parts by mass of the component (A). And the total content (parts by mass) of the component (B) and the component (C) relative to 100 parts by mass of the component (A) is the x-axis, the sum of the component (B) and the component (C) Point a where x = 83 (parts by mass) y = 88.9 (% by mass), x = 101 (parts by mass) when the content (% by mass) of the component (B) with respect to the content is y-axis ), Y = 80.0 (mass%) , X = 124 (part by mass), point c represented by y = 54.5 (mass%), point d represented by x = 101 (mass part), y = 90.0 (mass%), and A line segment ab, a line segment bc, a line segment ce, a line segment ed, and five points including a point e represented by x = 124 (mass part) and y = 72.7 (mass%) The content ratio of the component (B) with respect to the total content of the component (B) and the component (C) is present in the area of the figure composed of the line segment da.
Hereinafter, each component of the highly heat conductive resin composition of this invention is explained in full detail.

[(A) Polyarylene sulfide resin]
The polyarylene sulfide resin as the component (A) is a polymer compound mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit, and is generally known in the present invention. PAS resins having the molecular structure shown can be used.

  Examples of the arylene group include a p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, p, p′-. A diphenylene ether group, p, p'-diphenylenecarbonyl group, naphthalene group, etc. are mentioned. The PAS resin may be a homopolymer consisting only of the above repeating units, or a copolymer containing the following different types of repeating units may be preferable from the viewpoint of processability and the like.

  As the homopolymer, PPS using a p-phenylene sulfide group as an arylene group and a p-phenylene sulfide group as a repeating unit is preferably used. As the copolymer, among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. It is done. Of these, those containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide groups are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. The (A) PAS resin used in the present invention may be a mixture of two or more different molecular weight PAS resins.

  In addition to the linear PAS resin, a partially branched or crosslinked structure is formed by using a small amount of a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents when performing condensation polymerization. Examples thereof include polymers obtained by heating a polymer having a low molecular weight and a linear structure polymer having a low molecular weight at a high temperature in the presence of oxygen or the like to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving molding processability. However, since a polymer having a branched structure or a crosslinked structure has a decreased fluidity as the amount of the branched structure or the crosslinked structure is increased, it needs to be used with care.

The melt viscosity (310 ° C., shear rate 1216 sec ⁻¹ ) of the PAS resin as the base resin used in the present invention is preferably 200 Pa · s or less, including the above mixed system, and is in the range of 8 to 150 Pa · s. Those having a good balance between mechanical properties and fluidity are particularly preferred. When the melt viscosity exceeds 200 Pa · s, it becomes difficult to improve fluidity, and problems may occur.

[(B) Magnesium oxide previously surface-treated with vinylalkoxysilane compound]
In the present invention, (B) magnesium oxide pre-treated with a vinylalkoxysilane compound (hereinafter sometimes referred to as “surface-treated magnesium oxide”) provides high thermal conductivity and high thin-wall fluidity. Added. Thus, in this invention, although a vinyl alkoxysilane compound is used as a surface treatment agent of magnesium oxide, only when a vinyl alkoxysilane compound is used among alkoxysilane compounds, remarkable thin-walled fluidity is exhibited. In other words, even if magnesium oxide pre-treated with an alkoxysilane compound other than a vinylalkoxysilane compound is used, no remarkable thin-walled fluidity is exhibited. Processing is essential.

  (B) In the surface-treated magnesium oxide, the vinyl alkoxysilane compound used for the surface treatment is preferably a silane compound having one or more vinyl groups and two or three alkoxy groups in one molecule. A methoxysilane hydrolyzate, a vinyltriethoxysilane hydrolyzate, a vinyltris (β-methoxyethoxy) silane hydrolyzate and the like can be mentioned, among which a vinyltrimethoxysilane hydrolyzate is preferable.

  In this invention, it is preferable that the adhesion amount of the vinyl alkoxysilane compound with respect to magnesium oxide in the (B) surface treatment magnesium oxide surface is 0.3-1.5 mass%, and is 0.5-1 mass%. Is more preferable. When the adhesion amount of the vinyl alkoxysilane compound is 0.3 to 1.5% by mass, remarkable thin wall fluidity is exhibited.

(B) The average particle diameter (hereinafter, simply referred to as “average particle diameter”) of the surface-treated magnesium oxide measured by the laser diffraction / scattering method is more than 10 μm and not more than 100 μm from the viewpoint of further improving the thin-wall fluidity. Preferably, the thickness is 15 μm or more and 60 μm or less, and more preferably 25 μm or more and 50 μm or less.
In the present invention, the “average particle diameter measured by the laser diffraction / scattering method” means a particle diameter having an integrated value of 50% in the particle size distribution measured by the laser diffraction / scattering method.

  In the present invention, (B) surface-treated magnesium oxide and (C) glass fiber described later are used in combination at a predetermined content ratio, so that the effect is exhibited. Therefore, the component (B) is preferable. Since content cannot be prescribed | regulated independently, it mentions later with content of (C) glass fiber.

[(C) Glass fiber]
Although there is no restriction | limiting in particular as glass fiber used in this invention, For example, the fiber diameter of 5-15 micrometers (preferably 6-13 micrometers) can be used. Especially, since the intensity | strength after shaping | molding becomes high, a thing with a fiber diameter of 8-10 micrometers is especially preferable.
A commercially available glass fiber can be used for such a glass fiber used in the present invention. As what is marketed, for example, manufactured by Fuji Fiber Glass Co., Ltd., chopped glass fiber (CS 3DE-257, average fiber diameter: 6 μm), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747H, Average fiber diameter: 10 μm), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fibers (ECS03T-747, average fiber diameter: 13 μm), and the like.

In this invention, although the total content of (B) component and (C) component is 80-130 mass parts with respect to 100 mass parts of said (A) component, the said total content is less than 80 mass parts. When the amount exceeds 130 parts by mass, the bending strength or the thin wall fluidity is inferior. The total content of component (B) and component (C) is preferably 83 to 124 parts by mass, more preferably 90 to 124 parts by mass.

On the other hand, if the thermal conductivity is 0.6 W / m · K or more, it can generally be said to be a resin composition having good thermal conductivity. In order to make the thermal conductivity 0.6 W / m · K or more while maintaining the bending strength or thin wall fluidity, not only the total content of the component (B) and the component (C) is in the above range, It is necessary to satisfy the following conditions for the content of the component (B) with respect to the total content of the component (B) and the component (C).
That is, the total content (parts by mass) of the component (B) and the component (C) with respect to 100 parts by mass of the component (A) is the x-axis, and the total content of the component (B) with respect to the total content of the components (B) and (C). When the content (mass%) is the y-axis, point a represented by x = 83 (mass part), y = 88.9 (mass%), x = 101 (mass part), y = 80.0 Point b represented by (mass%), x = 124 (mass part), point c represented by y = 54.5 (mass%), x = 101 (mass part), y = 90.0 (mass) %), And a line segment ab and a line segment bc with five points consisting of a point e represented by x = 124 (parts by mass) and y = 72.7 (% by mass) as vertices. , Line segment ce, line segment ed, and line segment da, the content ratio of component (B) with respect to the total content of component (B) and component (C) To standing.

  FIG. 1 shows the total content (parts by mass) of the component (B) and the component (C) with respect to 100 parts by mass of the component (A) (B) relative to the total content of the components (B) and (C). It is a graph which uses the content rate (mass%) of a component as a y-axis, and the said points a-e are plotted. In FIG. 1, the content of the component (B) with respect to the total content of the component (B) and the component (C) in the figure composed of the line segment ab, line segment bc, line segment ce, line segment ed, and line segment da. Is present, the thermal conductivity can be 0.6 W / m · K or more while maintaining the bending strength or the thin-wall fluidity. Conversely, if the content of the component (B) is outside the figure, the thermal conductivity cannot be 0.6 W / m · K or more.

[(D) alkoxysilane compound]
In the present invention, in order to improve mechanical properties, (D) an alkoxysilane compound may be blended. However, when the (D) alkoxysilane compound is added, the fluidity is lowered. Therefore, when obtaining the mechanical characteristics, the fluidity is sacrificed. Therefore, as will be described later, the amount in the case of blending is preferably a small amount.

  (D) The alkoxysilane compound is not particularly limited, and examples thereof include alkoxysilanes such as epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, mercaptoalkoxysilane, and the like, one or more of these. Is used. In addition, as for carbon number of an alkoxy group, 1-10 are preferable, Most preferably, it is 1-4.

  Examples of the epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like.

  Examples of aminoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl)- Examples thereof include γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane.

  Examples of vinylalkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and the like.

  Examples of mercaptoalkoxysilanes include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Of these, epoxyalkoxysilane and aminoalkoxysilane are preferable, and γ-aminopropyltriethoxysilane is particularly preferable.

  In the present invention, the (D) alkoxysilane compound is preferably blended in an amount of 0.45 to 1.5 parts by weight, and 0.5 to 0.8 parts by weight, based on 100 parts by weight of the (A) PAS resin. Is more preferable.

[(E) Epoxy group-containing olefin copolymer]
In the present invention, in order to further improve toughness, it is preferable to contain (E) an epoxy group-containing olefin copolymer. (E) The epoxy group-containing olefin copolymer is not particularly limited. (E) Epoxy group containing olefin type copolymer can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (E) epoxy group-containing olefin copolymer include an olefin copolymer including a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. Among them, an olefin-based copolymer containing a structural unit derived from (meth) acrylic acid ester is preferred because a highly heat conductive resin composition (molded product) that exhibits particularly excellent toughness (bending fracture strain) can be obtained. . Hereinafter, (meth) acrylic acid ester is also referred to as (meth) acrylate. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In this specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid, and “(meth) acrylate” means both acrylate and methacrylate.

  The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene, and ethylene is particularly preferable. The α-olefin can be used alone or in combination of two or more. (E) When the epoxy group-containing olefin copolymer contains a structural unit derived from α-olefin, flexibility is easily imparted to the resin member. The softening of the resin member due to the provision of flexibility contributes to the improvement of toughness (bending fracture strain).

  The glycidyl ester of α, β-unsaturated acid is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable. The glycidyl ester of α, β-unsaturated acid can be used alone or in combination of two or more. (E) When the epoxy group-containing olefin copolymer contains a glycidyl ester of α, β-unsaturated acid, an effect of improving toughness (bending fracture strain) is easily obtained.

  The (meth) acrylic acid ester is not particularly limited. For example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-n-hexyl, acrylic Acrylic acid esters such as acid-n-octyl; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-n-amyl, methacrylic acid And methacrylates such as -n-octyl. Of these, methyl acrylate is particularly preferable. The (meth) acrylic acid ester can be used alone or in combination of two or more. The structural unit derived from (meth) acrylate contributes to improvement of toughness (bending fracture strain).

  Olefin copolymer containing a structural unit derived from α-olefin and a structural unit derived from a glycidyl ester of α, β-unsaturated acid, and an olefin copolymer containing a structural unit derived from (meth) acrylic acid ester The coalescence can be produced by performing copolymerization by a conventionally known method. For example, the copolymer can be obtained by performing copolymerization by a generally well-known radical polymerization reaction. The type of copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Examples of the olefin copolymer include polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyacrylate-2-ethylhexyl, polystyrene, polyacrylonitrile. An olefin-based graft copolymer in which acrylonitrile / styrene copolymer, butyl acrylate / styrene copolymer, or the like is chemically bonded in a branched or cross-linked structure may be used.

  The olefin-based copolymer used in the present invention can contain structural units derived from other copolymerization components as long as the effects of the present invention are not impaired.

  More specifically, examples of the (E) epoxy group-containing olefin copolymer include glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, and the like. A copolymer is preferred.

  Examples of the glycidyl methacrylate-modified ethylene copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate copolymer, and ethylene-glycidyl methacrylate-methyl acrylate copolymer. Among them, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is preferable because a particularly excellent metal resin composite molded body can be obtained. Particularly preferred. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include “Bond First” (manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymer and glycidyl ether-ethylene copolymer.

  In this invention, it is preferable to contain 5-15 mass parts with respect to 100 mass parts of (A) component from a viewpoint of improving the toughness (E) epoxy group containing olefin type copolymer, and 7-9 masses. It is more preferable to contain part.

[filler]
The high thermal conductive resin composition of the present invention is inorganic or inorganic in order to improve performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage), electrical properties, etc. within the range not impairing the effects of the present invention. An organic filler may be blended, and a fibrous, powdery, or plate-like filler is used depending on the purpose.

  Examples of the fibrous filler include inorganic fibrous materials such as boron fibers and potassium titanate fibers. High melting point organic fiber materials such as polyamide, fluororesin, and acrylic resin can also be used.

The granular fillers include quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, titanium oxide, and zinc oxide. Examples thereof include metal carbonates such as oxides, calcium carbonate, and magnesium carbonate, and metal sulfates such as calcium sulfate and barium sulfate.
Examples of the plate-like filler include mica and glass flakes.
The above inorganic fillers can be used alone or in combination of two or more.

[Other ingredients]
The highly thermally conductive resin composition of the present invention is a known substance generally added to a thermoplastic resin, that is, a colorant such as a flame retardant, a dye or a pigment, an antioxidant or an ultraviolet ray, as long as the effects of the present invention are not hindered. A stabilizer such as an absorbent, a lubricant, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to the required performance.

  The production of the high thermal conductive resin composition of the present invention includes (1) a method in which all raw materials are mixed and kneaded, and (2) an alkoxysilane compound is added to the PAS resin, and after melt-kneading, surface-treated magnesium oxide and glass fiber (3) After melting the PAS resin, the effect of the present invention is exhibited by any method, such as a method of adding a surface treated magnesium oxide and a filler obtained by adding an alkoxysilane compound to glass fibers. Since the mechanical strength is improved by the reaction between the PAS resin and the alkoxysilane compound, the alkoxysilane compound (2) is added to the PAS resin and melted so that the PAS resin and the alkoxysilane compound react more efficiently. After kneading, it is preferable to produce by a method of adding surface-treated magnesium oxide and glass fiber.

  The high thermal conductivity resin composition of the present invention obtained as described above is excellent in thin-wall fluidity, and therefore has high thermal conductivity and bending even if it is a small and complicated part or a thin-walled part. It can be easily molded while maintaining the characteristics. In addition, molded products obtained by injection molding, extrusion molding, blow molding, etc. using the high thermal conductive resin composition of the present invention have high moisture and heat resistance, chemical resistance, dimensional stability, flame resistance, and electrical insulation. And excellent heat dissipation. Taking advantage of this advantage, it can be suitably used for parts that radiate internally generated heat, such as automobile parts (motor periphery), electrical devices (LED heat sinks), heat exchangers, heat sinks, optical pickups, and the like.

  Other applications include, for example, LEDs, sensors, connectors, sockets, terminal blocks, printed circuit boards, motor parts, ECU cases and other electrical / electronic parts, lighting parts, TV parts, rice cooker parts, microwave oven parts, iron parts, etc. It can be used for household and office electrical product parts such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air conditioner parts.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Examples 1-6 , 8-12 , Comparative Examples 1-19 , Reference Example 1 ]
Each raw material component shown in Tables 1 to 7 was dry blended, then charged into a twin-screw extruder having a cylinder temperature of 320 ° C. (magnesium oxide was added separately from the side feed portion of the extruder), melt-kneaded, and pelletized. Only Examples 11 to 12 and Comparative Example 19 shown in Tables 7 and 8 contain (E) an epoxy group-containing olefin copolymer.
Various test pieces (depending on the evaluation items) were produced from the pellets by an injection molding machine and evaluated. The results are shown in Tables 1-7.
Note that points a to e in FIG. 1 correspond to Examples 1, 4, 10, 3, and 8, respectively.
Moreover, in Tables 1-8, "(B) component content rate" shows the content rate (mass%) of (B) component with respect to the total content of (B) component and (C) component.
Further, in Tables 1 to 8, the numerical values of the contents of the (B) component column and (C) component column are rounded off to the nearest decimal place, whereas “(B) component and (C In the column of “(Total component content)”, the numerical values obtained by calculating without rounding the numerical values of the respective components are listed. From such circumstances, in Tables 1 to 8, the sum of the numerical values in the (B) component column and (C) component column agrees with the “total content of (B) component and (C) component”. May not.
Details of each raw material component used in each example, comparative example, and reference example are shown below.

(A) PAS resin PPS resin: manufactured by Kureha Co., Ltd., Fortron KPS W203A (melt viscosity: 30 Pa · s (shear rate: 1216 sec ⁻¹ , 310 ° C.))
(B) Surface-treated magnesium oxide Magnesium oxide: RF-50-SC (Surface treatment: 0.5% by mass of vinylalkoxysilane) manufactured by Ube Materials Co., Ltd. (average particle size 50 μm)
(C) Glass fiber Chopped glass fiber manufactured by Nippon Electric Glass Co., Ltd. ECS03T-747H (average fiber diameter 10 μm)
(D) Alkoxysilane compound Alkoxysilane compound: γ-aminopropyltriethoxysilane: Shin-Etsu Chemical Co., Ltd., KBE-903P
(E) Epoxy group-containing olefin copolymer, manufactured by Sumitomo Chemical Co., Ltd., Bond First 7L

In each of the examples and comparative examples, the following test pieces were prepared and evaluated.
(1) Melt viscosity (A) About component (PPS resin), using a Capillograph manufactured by Toyo Seiki Co., Ltd., using a 1 mmφ × 20 mmL / flat die as a capillary, a barrel temperature of 310 ° C., and a shear rate of 1216 sec ⁻¹ The melt viscosity was measured.
About the prepared resin composition (the above-mentioned pellet), a Toyo Seiki Capillograph was used, and a 1 mmφ × 20 mmL / flat die was used as a capillary, and a melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1000 sec ⁻¹ was measured.
(2) Thin wall fluidity (thickness 0.5 mmt bar flow: 0.5 mmtBF)
A rod-shaped molded product having a width of 5 mm and a thickness of 0.5 mm was molded by injection molding under the conditions of a cylinder temperature of 320 ° C., an injection pressure of 100 MPa, and a mold temperature of 150 ° C., and the flow distance was measured. The average value in five tests was taken as the flow distance.
(3) Thermal conductivity A disk-shaped molded article having a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. and having a diameter of 30 mm and a thickness of 2 mm was produced by injection molding. Using a sample in which four test pieces were stacked, the thermal conductivity was measured with a hot disk method thermophysical property measuring apparatus (TPA-501, manufactured by Kyoto Electronics Industry Co., Ltd.).
(4) Bending strength and bending rupture strain By injection molding, a test piece (width 10 mm, thickness 4 mm) according to ISO 3167 was prepared at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and bending strength (FS) was determined according to ISO 178. ) And bending fracture strain (Fγ).

  On the other hand, in order to evaluate the relationship between the presence or absence of (E) component addition and “bending fracture strain (Fγ)”, Examples 11 and 12 and Comparative Example 19 to which (E) component was added, and (E) component were Table 8 below shows numerical values of “bending fracture strain (Fγ)” in Examples 1 and 3 to which no addition was made.

From Tables 1 to 8, the following can be understood.
In each of Examples 1 to 6 and Examples 8 to 12, excellent evaluation results were obtained in terms of thin-wall fluidity, thermal conductivity, and bending strength. In particular, in Examples 11 and 12 using the (E) epoxy group-containing olefin copolymer, compared with Examples 1 and 3 in which the total contents of the component (B) and the component (C) are the same, respectively. And excellent bending fracture strain (toughness). That is, it turns out that it is excellent in toughness by using the (E) epoxy group containing olefin type copolymer.
Comparative Example 1 in which the total content of the (B) component and the (C) component with respect to 100 parts by mass of the (A) component is less than 80 parts by mass is inferior in thermal conductivity, and the comparative example 15 in which the total content exceeds 130 parts by mass. -18 were inferior in bending strength or thin-wall fluidity.
When the thermal conductivity is 0.6 (W / m · K) or more, it can be generally said that the resin composition has good thermal conductivity, but both the component (B) and the component (C) were used. In this case, there is a relationship between the total content of the component (B) and the component (C) with respect to 100 parts by mass of the component (A) and the content of the component (B) with respect to the total content of the component (B) and the component (C). It can be seen that the thermal conductivity cannot be 0.6 (W / m · K) or more unless it is within the range specified in the present invention.
From the above, in order to have high bending strength while maintaining high thermal conductivity and excellent thin-wall fluidity, the total content of component (B) and component (C) with respect to 100 parts by mass of component (A) It turns out that it is necessary to make it into the range prescribed | regulated to this invention for the relationship with the content rate of (B) component with respect to the total content of (B) component and (C) component while setting it as 80-130 mass parts.

Claims (5)

(A) Polyarylene sulfide resin, (B) Magnesium oxide previously surface-treated with a vinylalkoxysilane compound, (C) Glass fiber, and (D) An alkoxysilane compound, an electrically insulating high thermal conductivity A resin composition comprising:
The total content of the component (B) and the component (C) is 80 to 130 parts by mass with respect to 100 parts by mass of the component (A), and the component (B) with respect to 100 parts by mass of the component (A). The total content (parts by mass) of the component and the component (C) is the x axis, and the content (mass%) of the component (B) relative to the total content of the component (B) and the component (C) is the y axis. , Point a represented by x = 83 (mass part), y = 88.9 (mass%), point represented by x = 101 (mass part), y = 80.0 (mass%) b, point c represented by x = 124 (mass part), y = 54.5 (mass%), point d represented by x = 101 (mass part), y = 90.0 (mass%), And a line segment ab, a line segment bc, and a line segment c, with five points consisting of a point e represented by x = 124 (parts by mass) and y = 72.7 (% by mass) as vertices. The content ratio of the component (B) with respect to the total content of the component (B) and the component (C) is present in the region of the figure composed of e, the line segment ed, and the line segment da. High thermal conductive resin composition.   The highly heat conductive resin composition of Claim 1 which contains 0.45-1.5 mass part of said (D) alkoxysilane compounds with respect to 100 mass parts of said (A) component.   Furthermore, (E) The highly heat conductive resin composition of Claim 1 or 2 which contains 5-15 mass parts of epoxy group containing olefin type copolymers with respect to 100 mass parts of said (A) component. The high heat according to claim 3, wherein the component (E) is an epoxy group-containing olefin copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. Conductive resin composition. The high thermal conductive resin composition according to claim 4, wherein the component (E) is an epoxy group-containing olefin copolymer further containing a structural unit derived from a (meth) acrylic acid ester.

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