JP6747934B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition having excellent thermal conductivity and antistatic property.

Polyphenylene ether resins are widely used as molding materials having excellent heat resistance, dimensional stability, and flame retardancy, such as electronic/electrical parts, OA equipment parts, audiovisual equipment parts, and automobile parts.

In recent years, due to the refinement of resin parts, parts that generate heat and static electricity are often installed in the vicinity of the resin parts or incorporated in a resin chassis or the like. However, since the polyphenylene ether resin has a low thermal conductivity and is an electrical insulating material, strength deterioration and dimensional change due to heat, dust adhesion due to electrification, and electrostatic discharge are caused by static electricity weak ICs, transistors, circuit boards, etc. It is a cause of causing extremely serious troubles such as destruction of the.
For this reason, many improvements have been proposed in which a good thermal conductive substance and a conductive substance are blended in terms of materials to impart thermal conductivity and antistatic properties.

As these techniques, a resin composition obtained by mixing polyarylene sulfide resin with metallic silicon powder, carbon fiber, graphite or the like (see, for example, Patent Document 1), a resin obtained by mixing a non-conductive inorganic filler and graphite with a thermoplastic resin A composition (see, for example, Patent Document 2) and the like have been proposed.
These documents devise techniques for imparting thermal conductivity and conductivity by blending various good thermal conductivity and conductive materials with a resin. However, the electrical conductivity of the resin composition obtained by the technology of imparting conductivity is largely different depending on the manufacturing method of the resin composition, the shape of the molded part, and the manufacturing method, and controlling them is an important technique in the resin composition. Has become.

Generally, the non-insulating resin composition provided with conductivity is classified as follows from the range of its surface resistivity.
(1) The conductive resin composition is 1×10 ⁵ Ω/sq. A resin composition having a surface resistivity of less than 1%, which causes a strong electrostatic discharge when a charged object comes into contact therewith and exhibits high conductivity (low resistance).
(2) The static dissipative resin composition has a density of 1×10 ⁵ to 1×10 ⁹ Ω/sq. It has a surface resistivity of, does not cause a strong electrostatic discharge when a charged object comes into contact with it, slowly diffuses the electric charge, and promptly dissipates the electric charge. It exhibits conductivity and can shield the electrostatic field. A resin composition having no conductivity.
(3) The antistatic resin composition has a viscosity of 1×10 ⁹ to 1×10 ¹⁴ Ω/sq. A resin composition having the above surface resistivity and having a conductivity capable of preventing charging itself to some extent, but not having a conductivity enough to rapidly dissipate static electricity of a charged object.
The non-insulating resin composition having these three electrical characteristics is appropriately selected and used from the range of its surface resistivity depending on the purpose and application.

Among these classifications, the surface resistivity is 1×10 ⁵ to 1×10 ⁹ Ω/sq. Area of the electrostatic diffusion resin composition or the surface resistivity of 1×10 ⁹ to 1×10 ¹⁴ Ω/sq. The antistatic resin composition of the region is obtained by blending various conductive materials when producing the composition, but the surface resistance value and the volume resistance value are greatly different, and the resistance value may be uniform. It was difficult. When used as a non-insulating resin molded product, an electrostatic diffusion resin composition and an antistatic resin composition having a measured surface resistance value-volume resistance value ratio close to 1 and a uniform resistance value are desired. However, at present, such a resin composition has not been obtained.

JP, 2007-146105, A International Publication No. 2007/114056

In Patent Documents 1 and 2, it is difficult to simultaneously improve the thermal conductivity and the uniform resistance value of a molded product, and a resin composition improved with these is desired.

The problem to be solved by the present invention is to provide a resin composition having excellent thermal conductivity, capable of controlling the surface resistivity in an electrostatic diffusion region or an antistatic region, and having a surface resistance value and a uniform resistance value with respect to a volume resistance value. is there.

In order to solve the above problems, the present inventors have conducted extensive studies, and as a result, a resin composition in which a specific amount of polyphenylene ether-based resin and metallic silicon powder is added is excellent in thermal conductivity, and surface resistivity is specified. The inventors have found that the resistance can be controlled to be uniform and the resistance value is uniform, and have reached the present invention.

That is, the present invention is as follows.
[1]
(A) 35 to 90% by mass of polyphenylene ether resin,
(B) 10 to 60 mass% of metallic silicon powder,
(C) 0 to 50 mass% of flake graphite,
(D) a condensed phosphoric acid ester-based flame retardant as an optional component,
Made (with the proviso that said component (a), the component (b), the component (c), and the total amount of the component (d) is 100 mass%),
The content of polyphenylene ether in the component (a) is 10 to 51.4 mass %,
A resin composition comprising:
[2]
The resin composition according to [1], wherein the content of the polyphenylene ether in the resin composition is 10 to 40.5% by mass.

[3]
Wherein component (a), a polyphenylene ether, including at least one thermoplastic resin selected from the group consisting of crystalline resin and amorphous resin, [1] or the resin composition according to [2] ..

[4]
The crystalline resin is at least one selected from the group consisting of polyolefin, syndiotactic polystyrene, polyacetal, polyamide, polyester, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, and fluororesin,
The resin according to [3] , wherein the non-crystalline resin is at least one selected from the group consisting of atactic polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, polyamideimide, and polyetherimide. Composition.

[5]
The resin composition according to any one of [1] to [4] , wherein the component (b) is metallic silicon powder having an average particle size of 8 to 25 μm.

[6]
The resin composition according to any one of [1] to [5] , wherein the component (c) is flake graphite having an average particle diameter of 120 to 700 μm.

[7]
In [1] to [6] , the mass ratio between the component (b) and the component (c) (mass of the component (b)/mass of the component (c)) is 20/80 to 80/20 . The resin composition described.

[8]
6 to 20 mass% of the condensed phosphoric acid ester-based flame retardant (d) is contained with respect to 100 mass% of the total of the component (a), the component (b), the component (c), and the component (d). The resin composition according to any one of [1] to [7] .

[9]
The resin composition according to any one of [1] to [8] , wherein the component (a) contains a polymer alloy of polyphenylene ether and atactic polystyrene.

[10]
The resin composition according to any one of [1] to [8] , wherein the component (a) is a polymer alloy of polyphenylene ether and polyphenylene sulfide.

[11]
The resin composition according to any one of [1] to [8] , wherein the component (a) is a polymer alloy of polyphenylene ether and polyolefin.

[12]
The resin composition according to any one of [1] to [8] , wherein the component (a) is a polymer alloy of polyphenylene ether and polyamide.

[13]
The resin composition according to any one of [1] to [8] , wherein the component (a) is a polymer alloy of polyphenylene ether and polyester.

According to the present invention, the thermal conductivity is excellent, the surface resistivity can be controlled in the static electricity diffusion region or the antistatic region, and the surface resistance value and the volume resistance value have a uniform resistance value (ratio between the surface resistance value and the volume resistance value). Can be provided.

FIG. 1 is a schematic diagram (plan view) showing measurement points at the time of measuring warpage in Examples and Comparative Examples.

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments and can be variously modified and implemented within the scope of the gist.

[Resin composition]
The resin composition of the present embodiment contains (a) a polyphenylene ether resin and (b) a metal silicon powder, and optionally (c) scaly graphite and (d) a condensed phosphate ester-based flame retardant. Including. In the resin composition of the present embodiment, the content of the component (a) is relative to the total mass (100 mass%) of the component (a), the component (b), the component (c), and the component (d). 35 to 90% by mass, the content of the component (b) is 10 to 60% by mass, and the content of the component (c) is 0 to 50% by mass.
Since the resin composition of the present embodiment has the above-mentioned configuration, it has excellent thermal conductivity, can control the surface resistivity within a specific range, and exhibits a uniform resistance value. Further, it is possible to exhibit an excellent balance of physical properties in heat resistance, dimensional accuracy, and flame retardancy.
In addition, in this specification, polyphenylene ether may only be called "PPE."

The constituent components of the resin composition of this embodiment will be described below.
((A) Polyphenylene ether resin)
The (a) polyphenylene ether-based resin contains at least polyphenylene ether, and optionally a thermoplastic resin, an admixture and the like. That is, the component (a) may be a polyphenylene ether alone or a mixture containing a polyphenylene ether and a thermoplastic resin.
Here, the content of the polyphenylene ether in the component (a) is preferably 5% by mass or more, and more preferably 10% by mass or more, from the viewpoint of flame retardancy, dimensional accuracy, and heat resistance. The content of polyphenylene ether in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of flame retardancy, dimensional accuracy and heat resistance.

-Polyphenylene ether-
Since the component (a) contains polyphenylene ether, the resin composition of this embodiment has excellent flame retardancy, dimensional accuracy, and heat resistance.

上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜７の第１級アルキル基、炭素数１〜７の第２級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択される一価の基である。 Examples of PPE include a homopolymer having a repeating unit structure represented by the following formula (1) and/or a copolymer having a repeating unit structure represented by the following formula (1).
The PPE may be used alone or in combination of two or more.

In the above formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a primary alkyl group having 1 to 7 carbon atoms. Selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbon oxy groups, and halohydrocarbonoxy groups having at least two carbon atoms separating a halogen atom and an oxygen atom. It is a monovalent group.

From the viewpoint of fluidity, toughness and chemical resistance during processing, the polyphenylene ether has a reduced viscosity measured with an Ubbelohde type viscous tube under the condition of 30° C. using a chloroform solution having a concentration of 0.5 g/dL. , 0.15 to 2.0 dL/g is preferable, 0.20 to 1.0 dL/g is more preferable, and 0.30 to 0.70 dL/g is further preferable.

The PPE is not limited to the following, but examples thereof include poly(2,6-dimethyl-1,4-phenylene ether) and poly(2-methyl-6-ethyl-1,4-phenylene ether). , Poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether) and other homopolymers, 2,6-dimethylphenol and other phenols Examples thereof include a copolymer with a class (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). Among them, poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethyl from the viewpoint of balance between toughness and rigidity and availability of raw materials. A copolymer with phenol is preferable, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferable.

The PPE can be manufactured by a known method. The method for producing PPE is not limited to the following, but, for example, 2,6-xylenol is used as a catalyst using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874. Method of oxidative polymerization, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, JP-A-63. The methods described in Japanese Patent Publication No. 152628/1990 and the like can be mentioned.

The PPE is a modified PPE obtained by reacting the homopolymer and/or the copolymer with a styrene-based monomer or a derivative thereof, and/or an α,β-unsaturated carboxylic acid or a derivative thereof. It may be. Here, the grafting amount or addition amount of the styrene-based monomer or its derivative and/or the α,β-unsaturated carboxylic acid or its derivative is 0.01 to 10% by mass with respect to 100% by mass of the modified PPE. It is preferable.

Examples of the method for producing the modified PPE include a method of reacting in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at a temperature of 80 to 350°C.
As the PPE, a mixture of the homopolymer and/or the copolymer and the modified PPE in an arbitrary ratio may be used.

-Thermoplastic resin-
The component (a) may further contain a thermoplastic resin.
The thermoplastic resin can be classified into a crystalline resin and an amorphous resin. As the thermoplastic resin, at least one kind of thermoplastic resin can be selected regardless of whether it is a crystalline resin or an amorphous resin, and it can be used in combination with polyphenylene ether. The component (a) preferably contains, for example, the above polyphenylene ether and at least one thermoplastic resin selected from the group consisting of a crystalline resin and an amorphous resin, and the polyphenylene ether and the crystalline resin are included. And the like, a polymer alloy of a combination of polyphenylene ether and an amorphous resin, a polymer alloy of a combination of polyphenylene ether, a crystalline resin and an amorphous resin, and the like.

In the component (a), the mass ratio between the polyphenylene ether and the thermoplastic resin (mass of polyphenylene ether/mass of thermoplastic resin) is 99/1 to 1/99 when the thermoplastic resin is a polystyrene resin. It is more preferably 98/2 to 5/95, further preferably 90/10 to 5/95. When the thermoplastic resin is other than polystyrene resin, it is preferably 99/1 to 1/99, more preferably 80/20 to 5/95, and further preferably 40/60 to 5/95.

Examples of the crystalline resin include at least one selected from the group consisting of polyolefin, syndiotactic polystyrene, polyacetal, polyamide, polyester, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, and fluororesin. .. Examples of the crystalline resin also include polyoxymethylene copolymers.
Examples of the non-crystalline resin include at least one selected from the group consisting of atactic polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, polyamideimide, and polyetherimide.
Among them, thermoplastic resins that are preferably used include polyolefin, syndiotactic polystyrene, polyacetal, polyamide, polyester, polyphenylene sulfide, atactic polystyrene and the like.
The crystalline resin and the amorphous resin may be used alone or in combination of two or more.
The crystalline resin means a resin having a crystal peak when measured by DSC (differential scanning calorimeter), and the non-crystalline resin means a resin having no crystal peak.

Examples of the polyolefin include polypropylene such as isotactic polypropylene; poly(4-methyl-1-pentene); polybutene-1; high density polyethylene, ultra high molecular weight high density polyethylene, low density polyethylene, linear low density polyethylene, density Polyethylene such as ultra-low density polyethylene of less than 0.90; ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/octene copolymer, propylene/ethylene copolymer (random copolymer or block copolymer Copolymers), propylene/1-hexene copolymers, propylene/4-methyl-1-pentene copolymers, etc., and copolymers composed of two or more α-olefins selected from α-olefins such as ethylene and propylene. Coalescing; and the like.

The syndiotactic structure in the syndiotactic polystyrene means that the stereochemical structure is a syndiotactic structure, that is, a phenyl group that is a side chain is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure, and its stereoregularity (tacticity) can be quantified by a nuclear magnetic resonance method ( ¹³ C-NMR) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method may be indicated by the abundance ratio of a plurality of continuous monomer units, for example, two diads, three triads, and five pentads. it can.

The syndiotactic polystyrene preferably has a racemic dyad of 75% or more, more preferably 85% or more, or preferably 30% or more, more preferably 50% or more of racemic pendat syndiotacticity. Polystyrene, poly (alkyl styrene), poly (vinyl styrene), poly (aryl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), these Examples of the hydrogenated polymer, a mixture thereof, a copolymer containing a styrene-based monomer unit constituting these polystyrenes as a main component, and the like.
Examples of the poly(alkylstyrene) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), and the like.
Examples of the poly(vinylstyrene) include poly(vinylnaphthalene), poly(vinylstyrene), poly(divinylbenzene), and the like.
Examples of the poly(aryl styrene) include poly(phenyl styrene).
Examples of the poly(halogenated styrene) include poly(chlorostyrene), poly(bromostyrene), poly(fluorostyrene) and the like.
Examples of the poly(halogenated alkylstyrene) include poly(chloromethylstyrene).
Examples of the poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene).
Among them, polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(ethylstyrene), poly(divinylbenzene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), Poly(m-chlorostyrene), poly(p-fluorostyrene) and hydrogenated polystyrene are preferred.

The syndiotactic polystyrene is, for example, in the presence or absence of an inert hydrocarbon solvent, using a condensation product of a titanium compound and water and a trialkylaluminum as a catalyst, a styrene monomer (the styrene polymer Can be produced by polymerizing (monomer corresponding to the above) (JP-A-62-187708). Further, poly(halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and hydrogenated polymer can be obtained by the method described in JP-A-1-178505.

Examples of comonomers used with the above-mentioned styrene-based polymer monomer in the above-mentioned syndiotactic polystyrene copolymer include olefin monomers such as ethylene, propylene, butene, hexene, and octene; diene monomers such as butadiene and isoprene; Cyclic diene monomers; polar vinyl monomers such as methyl methacrylate, maleic anhydride and acrylonitrile; and the like.
Particularly, a copolymer having 80 to 100 mol% of styrene repeating units and 0 to 20 mol% of p-methylstyrene repeating units is preferably used.

The weight average molecular weight of the syndiotactic polystyrene is preferably 150,000 to 300,000. Within the above range, the workability during film formation will be good.
The weight average molecular weight can be measured using GPC (mobile layer: chloroform, standard substance: polystyrene).

Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6/6,12, and polyamide MXD. (M-xylylenediamine)/6, polyamide 6,T, polyamide 6,I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6/6, T, polyamide 6,6/6, I, polyamide 6/6, T/6, I, polyamide 6,6/6, T/6, I, polyamide 6/12/6, T, polyamide 6,6/12/6,T, polyamide 6/12 /6,I, Polyamide 6,6/12/6,I, Poly(Varaphenylene terephthalamide), Poly(Varabenzamide), Poly(4,4'-benzanilide terephthalamide), Poly(Varaphenylene-4, 4'-biphenylene dicarboxylic acid amide), poly(valaphenylene-2,6-naphthalene dicarboxylic acid amide), poly(2-chloro-valaphenylene terephthalamide), varaphenylenediamine/2,6-dichloroparaphenylenediamine/terephthalate Examples thereof include acid dichloride copolymers and polynonamethylene terephthalamide (9T nylon).

Examples of the polyester include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and the like. Among them, polytrimethylene terephthalate and polybutylene terephthalate are preferable.

As the polyphenylene sulfide (hereinafter sometimes referred to as PPS), the repeating unit of the arylene sulfide represented by the following formula (2) is preferably 50 mol%, more preferably 70 mol%, and further preferably 90 mol%. %, and the like.
[-Ar-S-] (2)
(In the formula (2), Ar is a p-phenylene group, m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms, a phenyl group), p,p'-di. It shows an arylene group such as a phenylene sulfone group, a p,p'-biphenylene group, a p,p'-diphenylenecarbonyl group, and a naphthylene group.)

The PPS may be a homopolymer composed of one type of repeating unit represented by the above formula (2), or two or more types represented by the above formula (2) from the viewpoint of processability and heat resistance. It may be a copolymer comprising a repeating unit of. Among them, linear polyphenylene sulfide having a repeating unit of p-phenylene sulfide as a main constituent unit is preferable because it is excellent in processability and heat resistance and is easily available industrially.

The method for producing PPS is, for example, a method in which a halogen-substituted aromatic compound such as p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, or sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent. And a method of polymerizing in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, a method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is preferable. Examples of the method for producing PPS include US Pat. No. 2,513,188, JP-B-44-27671, JP-B-45-3368, JP-B-52-12240, JP-A-61-225217, and US Pat. Japanese Patent No. 3274165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-222196, etc., and the prior art methods exemplified in these patents, etc. Is mentioned.

After the polyphenylene sulfide is polymerized by the above-mentioned method, a cross-linked PPS in which the molecular weight and the viscosity are appropriately increased by heating the polyphenylene sulfide at a temperature below the melting point of the polyphenylene sulfide in the presence of oxygen to promote oxidative crosslinking is also suitable. Can be used.

As the PPS, a linear PPS and a crosslinked PPS may be used in combination at any ratio.

Examples of the atactic polystyrene include rubber-reinforced polystyrene (HIPS), styrene-acrylonitrile copolymer (AS) having a styrene content of at least 50% by weight, and rubber-reinforced AS resin thereof.

In the case where the component (a) is a polymer alloy obtained by heat-melt mixing or solution mixing of polyphenylene ether and one or more other resins, an admixture may be added when the polymer alloy is obtained. Good. The admixture may be used alone or in combination of two or more.
As the above-mentioned admixture, for example, in the case of a polymer alloy of polyphenylene sulfide/polyphenylene ether, an epoxy resin, a silane coupling agent, a styrene-glycidyl methacrylate copolymer, a copolymer of styrene and 2-isopropenyl-2-oxazoline. , Styrene-maleic anhydride copolymer resins; 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl-4,4'- Examples thereof include polyisocyanate compounds such as diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenylene polyisocyanate. Further, in the case of a polymer alloy of polyolefin/polyphenylene ether, a hydrogenated block copolymer, a block copolymer having a polyolefin chain/polystyrene chain, a graft copolymer, or the like can be used as an admixture. In the case of a polyamide/polyphenylene ale polymer alloy, a styrene-maleic anhydride copolymer, a styrene-glycidyl methacrylate copolymer, a copolymer of styrene and 2-isopropenyl-2-oxazoline, a polyphenylene grafted with maleic anhydride Ether can be used as an admixture. In the case of a polyester/polyphenylene ether polymer alloy, a resin such as a styrene-glycidyl methacrylate copolymer or a copolymer of styrene and 2-isopropenyl-2-oxazoline; 2,4-toluylene diisocyanate, 2,6-toluene. Polyisocyanate compounds such as diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylene polyisocyanate; etc. are used as admixtures it can.
The polymer alloy that can be used as the component (a) is not limited to the above-mentioned polymer alloy.

The content of the component (a) in the resin composition of the present embodiment is a value when the total amount of the component (a), the component (b), the component (c), and the component (d) is 100% by mass. From the viewpoint of heat resistance, heat resistance, impact resistance and flame retardancy, it is 35 to 90% by mass, preferably 40 to 90% by mass, more preferably 45 to 90% by mass, and further preferably 50 to 90% by mass. is there. When the content of the component (a) is in the range of 40 to 90% by mass, the workability, heat resistance and flame retardancy can be sufficiently balanced.

((B) Metallic silicon powder)
The resin composition of the present embodiment contains metallic silicon powder as the component (b). By containing the metallic silicon powder, the resin composition of the present embodiment has excellent thermal conductivity, and the surface resistivity can be controlled in the electrostatic diffusion region or the antistatic region.
In the present specification, "powder" refers to powder (particles) having no extreme difference in length, width, and length in the thickness direction. Specifically, when the minimum length of the particle dimensions is the x-direction length, and the directions perpendicular to the x-direction are the y-direction and the z-direction (x, y, and z are three-dimensional orthogonal to each other, respectively). (Orthogonal axis), the length in the x direction/the length in the y direction is 0.5 to 1.0, and the length in the x direction/the length in the z direction is 0.5 to 1.0.
The component (b) may be a mixture of powders having different shapes and particle sizes. In the present specification, the metallic silicon powder is preferably metallic silicon substantially free of non-powdered metallic silicon, and is a mixture of metallic silicon in which the non-powdered metallic silicon content is 5% by mass or less. More preferably.

The component (b) is not limited to the following, but any component that is conventionally known and sold and belongs to this category can be used.
From the viewpoint of thermal conductivity, the silicon content in the above-mentioned metallic silicon powder is preferably 95% by mass or more, and more preferably 98% by mass or more.

From the viewpoint of mechanical properties, fluidity, thermal conductivity, and non-insulating property, the metal silicon powder preferably has an average particle diameter (D ₅₀ ) measured by a laser diffraction scattering method of 8 to 25 μm, and more preferably It is preferably 10 to 20 μm. The average particle size is preferably in the above range not only as a raw material but also in a resin composition after kneading and a molded product of the resin composition.

Examples of the shape of the metal silicon powder include dendritic, scaly, spherical, acicular, polyhedral shapes such as cubic and dodecahedron shapes, and preferably scaly and spherical shapes. Also, a mixture of these shapes may be used.

The method for producing the above-mentioned metallic silicon powder is not particularly limited, but examples thereof include an electrolysis method, a mechanical pulverization method, an atomizing method, a heat treatment method, and a chemical production method.

The content of the component (b) in the resin composition of the present embodiment is a heat content when the total amount of the component (a), the component (b), the component (c), and the component (d) is 100% by mass. From the viewpoint of conductivity, non-insulating property, workability, heat resistance and impact resistance, it is 10 to 60% by mass, preferably 10 to 55% by mass, and more preferably 10 to 50% by mass. When the content of the component (b) is in the range of 10 to 60% by mass, the balance of thermal conductivity, non-insulating property, workability, heat resistance and impact resistance can be made sufficiently good. ..

((C) Flake graphite)
Since the resin composition of the present embodiment contains (c) scaly graphite, more excellent thermal conductivity can be obtained, the electric resistance value can be adjusted to a desired value, and the thermal conductivity of a wider range can be obtained. The effect of insulation performance can be obtained.
In addition, in the present specification, the term “scaly” refers to a flat shape in which the shape of the particles has a shorter distance in the thickness direction than the shorter distance in the length direction or the width direction. Specifically, the observation direction that maximizes the projected area is the thickness direction, the direction that is the major axis of the projection surface and is orthogonal to the thickness direction is the length direction, and the direction orthogonal to the length direction and the thickness direction is When referred to in the width direction, it means a shape in which the length in the width direction is 3 times or more (preferably 4 times or more, more preferably 10 times or more) with respect to the length in the thickness direction. The lengths in the length direction, the width direction, and the thickness direction can be measured by, for example, embedding graphite in a resin or the like, cutting it, and observing it with an optical microscope or the like.
The component (c) may be a mixture of graphites having different shapes and particle sizes. In the present specification, the scaly graphite is preferably graphite that does not substantially contain non-scaly graphite, and is more preferably a mixture of graphite in which the content of non-scaly graphite is 10% by mass or less. preferable.

The fixed carbon of the flake graphite is preferably 90% or more, more preferably 95% or more. The fixed carbon can be measured according to (JIS M8511).
The flake graphite may be artificial graphite or natural graphite.

The average particle size of the scaly graphite is preferably 120 to 700 μm, more preferably 130 to 500 μm, from the viewpoint of fluidity, thermal conductivity and non-insulating property.
The average particle size of the flake graphite can be measured by a sieve analysis method according to JIS M8511 “Industrial analysis and test method of natural graphite”. The average particle size is preferably in the above range not only as a raw material but also in a resin composition after kneading and a molded product of the resin composition.

The shape of the flake graphite is preferably a flat shape such as a plate shape, a flake shape, or a flake shape. The shape of the flake graphite does not include fibrous shape.

The flake graphite can be obtained by using natural graphite or artificial graphite by a mechanical pulverizing method, for example, a pulverizer such as a Glen mill, a Victory mill, a stamp mill, a ball mill, a jet mill, or a high speed rotary mill. The scaly graphite obtained by these methods was further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aliphatic metal salt in order to enhance the dispersion effect in the resin. It may be a material, an organic material treated with an ammonium salt or the like by an intercalation method, or a material treated with a resin such as a urethane resin or an epoxy resin as a binder.

The content of the component (c) in the resin composition of the present embodiment is a thermal conductivity when the total amount of the component (a), the component (b), the component (c), and the component (d) is 100% by mass. From the viewpoints of properties, non-insulating properties, workability, heat resistance, and impact resistance, it is 0 to 50% by mass, preferably 2 to 48% by mass, and more preferably 5 to 45% by mass. When the content of the component (c) is in the range of 0 to 50% by mass, the balance of thermal conductivity, non-insulating property, workability, heat resistance and impact resistance can be made sufficiently good.

When the resin composition of the present embodiment contains the component (c), the mass ratio of the component (b) and the component (c) (mass of the component (b)/mass of the component (c)) depends on workability and From the viewpoint of the balance of impact resistance and flame retardancy, it is preferably 20/80 to 80/20, more preferably 25/75 to 75/25.

((D) Condensed phosphate ester flame retardant)
The resin composition of the present embodiment may include (d) a condensed phosphoric acid ester-based flame retardant. By including the component (d), the auxiliary flame-retardant effect of the polyphenylene ether-based resin of the component (a) and the flame-retardant imparting effect of the component (d) are combined, so that the resin composition of the present embodiment is flame retarded. Has a great effect on imparting sex.

式（３）中、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール置換アルキル基、アリール基、ハロゲン置換アリール基、及びアルキル置換アリール基からなる群より選ばれる一価の基を表す。Ｘは、アリーレン基を表す。ｎは０〜５の整数である。
なお、上記ｎが異なるリン酸エステル及び／又はその縮合物である場合、上記ｎはそれらの平均値を表す。ｎ＝０である場合は、式（３）の化合物は、リン酸エステル単量体を示す。 The condensed phosphoric acid ester flame retardant is not limited to the following, but for example, a phosphoric acid ester represented by the following formula (3) and/or a condensate thereof can be used.

In formula (3), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, an aryl group, a halogen-substituted aryl group, And a monovalent group selected from the group consisting of alkyl-substituted aryl groups. X represents an arylene group. n is an integer of 0-5.
In addition, when said n is a different phosphoric ester and/or its condensate, said n represents those average values. When n=0, the compound of formula (3) represents a phosphate ester monomer.

Representative phosphoric acid ester monomers include, but are not limited to, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and the like.

As the condensate of the above phosphoric acid ester, n can take an average value of 1 to 5, but is preferably an average value of 1 to 3.

Further, from the viewpoint of flame retardancy and heat resistance exhibited when kneaded with another resin, it is preferable that at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is an aryl group, and all of them are aryl groups. More preferably, it is an aryl group. From the same viewpoint, preferable aryl groups include phenyl, xylenyl, cresyl, and halogenated derivatives thereof.

Examples of the arylene group of X include a residue in which two hydroxyl groups are eliminated from resorcinol, hydroquinone, bisphenol A, biphenol or a halogenated derivative thereof.

Examples of the condensation type phosphoric acid ester compound include, but are not limited to, resorcinol-bisphenyl phosphate compound, bisphenol A-polyphenyl phosphate compound, and bisphenol A-polycresyl phosphate compound.

The content of the component (d) in the resin composition of the present embodiment is a flow rate when the total amount of the component (a), the component (b), the component (c), and the component (d) is 100% by mass. From the viewpoint of heat resistance, heat resistance and flame retardancy, it is preferably 6 to 20% by mass, more preferably 8 to 20% by mass, and further preferably 10 to 18% by mass. When the content of the component (d) is in the range of 6 to 20% by mass, the balance of fluidity, heat resistance and flame retardancy can be made sufficiently more satisfactory.

The total amount of the component (a) and the component (d) in the resin composition of the present embodiment is (a) component, (b) component, (c) component, and ( When the total amount of component d) is 100% by mass, it is preferably 3 to 30% by mass, more preferably 5 to 25% by mass.

(Other ingredients)
In addition to the above-mentioned components, the resin composition of the present embodiment may have a thermal conductivity, an electric resistance value, a fluidity, a low volatile component, heat resistance and flame retardancy of the resin composition as long as necessary. And may contain other components.

Examples of the above-mentioned other components include, but are not limited to, thermoplastic elastomers (hydrogenated block copolymers and polyolefin elastomers), heat stabilizers, antioxidants, metal deactivators, crystals. Nucleating agent, flame retardant (organic phosphate compound not corresponding to component (d), ammonium polyphosphate compound, silicone flame retardant, etc.), plasticizer (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid ester) Etc.), weather (light) resistance improvers, slip agents, inorganic or organic fillers and reinforcing materials (polyacrylonitrile fiber, aramid fiber, etc.), various colorants, and release agents.

The resin composition of the present embodiment preferably contains no carbon fiber from the viewpoint of resistivity, warpage, and flame retardancy. The content of carbon fibers in the resin composition is, for example, 5% by mass or less.

The resin composition of the present embodiment has a surface resistivity of 1×10 ⁵ to 1×10 ¹⁴ Ω when formed into a molded plate having a length of 75 mm, a width of 75 mm, and a thickness of 3 mm, from the viewpoint of having an appropriate conductivity. /Sq. Is more preferable, and more preferably 1×10 ⁵ to 1×10 ¹² Ω/sq. Is.
Further, the resin composition of the present embodiment preferably has a surface resistance value of 3×10 ^{3 to} 3×10 ¹² Ω when formed into a molded plate having a length of 75 mm, a width of 75 mm and a thickness of 3 mm, and more preferably It is preferably 3×10 ^{3 to} 3×10 ¹⁰ Ω.
The surface resistivity and the surface resistance value can be measured by the methods described in Examples below.

The resin composition of the present embodiment has a volume resistance value of 1×10 ³ to 1×10 ¹⁴ Ω when used as a molded plate having a length of 75 mm, a width of 75 mm, and a thickness of 3 mm, from the viewpoint of having appropriate conductivity. Is preferable, and more preferably 1×10 ⁴ to 1×10 ¹² Ω.
The volume resistance value can be measured by the method described in Examples below.

The resin composition of the present embodiment preferably has an anisotropy of resistance value (surface resistance value/volume resistance value) close to 1, from the viewpoint of obtaining a molded article having a uniform resistance value. , 0.1 to 1.2 are preferable, and 0.3 to 1.2 are more preferable.

From the viewpoint of heat dissipation, the resin composition of the present embodiment preferably has a thermal conductivity of 0.1 W/m·K when formed into a molded plate having a length of 75 mm, a width of 75 mm, and a thickness of 3 mm. More preferably, it is 0.3 W/mK or more.

[Method for producing resin composition]
The resin composition of the present embodiment can be produced by melt-kneading the components (a) and (b), and optionally the components (c), (d) and other components.

The melt-kneader for performing melt-kneading is not limited to the following, and examples thereof include a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender plastograph, and a heating melt-kneader using a Banbury mixer. A twin-screw extruder is particularly preferable from the viewpoint of kneading property. Specific examples thereof include ZSK series manufactured by WERNER & PFLEIDER, TEM series manufactured by Toshiba Machine Co., Ltd., TEX series manufactured by Japan Steel Works, Ltd., and the like.

A preferred manufacturing method using an extruder will be described below.

L/D (effective barrel length/barrel inner diameter) of the extruder is preferably 20 or more and 60 or less, and more preferably 30 or more and 50 or less.

The configuration of the extruder is not particularly limited, but for example, with respect to the flow direction of the raw material, the first raw material supply port is provided on the upstream side, the first vacuum vent is provided downstream from the first raw material supply port, and the first vacuum vent is provided. A second raw material supply port is provided downstream (if necessary, third and fourth raw material supply ports may be further provided downstream of the second raw material supply port), and further downstream of the second raw material supply port. The one provided with the second vacuum vent is preferable. Particularly, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and between the second to fourth raw material supply ports and the second vacuum vent. It is more preferable to provide a kneading section.

The method for supplying the raw materials to the second to fourth raw material supply ports is not particularly limited, but the extruder side opening is more than the simple addition supply from the opening ports of the extruder second to fourth raw material supply ports. A method of feeding from the mouth using a forced side feeder tends to allow more stable feeding, which is preferable.

In particular, when the raw material contains powder and it is desired to reduce the generation of cross-linked products and carbides due to the heat history of the resin, the method using a forced side feeder supplied from the extruder side is more preferable, and the forced side feeder is It is more preferable that the method is provided at the fourth raw material supply port and the powder of these raw materials is divided and supplied.

Further, when adding a liquid raw material, a method of using a plunger pump, a gear pump or the like to add the raw material into the extruder is preferable.

The upper opening of the extruder second to fourth raw material supply ports can also be used as an opening for removing the air to be carried.

The melt-kneading temperature in the melt-kneading step of the resin composition, the screw rotational speed is not particularly limited, in the crystalline resin is heated above the melting point temperature of the crystalline resin, in the amorphous resin heating above the glass transition temperature The temperature at which the resin can be melted and processed without difficulty can be selected. Usually, the temperature is arbitrarily selected from 200 to 370° C., and the screw rotation speed is 100 to 1200 rpm.

As one of the specific production aspects of the resin composition of the present embodiment using a twin-screw extruder, for example, a polyphenylene ether resin as the component (a) is added to the first raw material supply port of the twin-screw extruder. It is supplied, the heating and melting zone is set to the melting temperature of the polyphenylene ether-based resin, and the mixture is melt-kneaded at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm, and in the state where the component (a) is melt-kneaded, biaxial extrusion A method of supplying the metallic silicon powder of the component (b), the flake graphite, and the condensed phosphoric acid ester-based flame retardant from the second raw material supply port of the machine and further melt-kneading can be mentioned. Further, the positions where the components (b), (c), and (d) are supplied to the twin-screw extruder may be collectively supplied from the second raw material supply port of the extruder as described above, A second raw material supply port, a third raw material supply port, and a fourth raw material supply port may be provided to supply each component separately.

Furthermore, in order to reduce the generation of crosslinked products and carbides due to heat history in the presence of oxygen in the resin, the oxygen concentration of each process line in the addition route of each raw material to the extruder is maintained at less than 1.0% by volume. It is preferable. The addition route is not particularly limited, but specific examples thereof include a configuration such as a stock tank in order, a pipe, a weight type feeder having a refill tank, a pipe, a supply hopper, and a twin-screw extruder. The method for maintaining the low oxygen concentration as described above is not particularly limited, but a method of introducing an inert gas into each process line having enhanced hermeticity is effective. Usually, it is preferable to introduce nitrogen gas to maintain the oxygen concentration below 1.0% by volume.

In the method for producing a resin composition described above, when the polyphenylene ether resin as the component (a) contains a powdery component (volume average particle diameter is less than 10 μm), the resin composition of the present embodiment is processed by a twin-screw extruder. When produced using, it brings about the effect of further reducing the residue in the screw of the twin-screw extruder, and further, in the resin composition obtained by the above-mentioned production method, reduces the occurrence of black spot foreign matters, carbides, etc. Bring effect.

As a specific method for producing the resin composition of the present embodiment, an extruder in which the oxygen concentration of each raw material supply port is controlled to be less than 1.0 volume% is used, and any one of the following methods 1 to 3 is performed. Preferably.
1. All or part of the component (a) contained in the resin composition of the present embodiment is melt-kneaded (first kneading step), and the component (a) is added to the kneaded product in the molten state obtained in the first kneading step. And the total amount of the components (b) to (d) are continuously supplied, and melt kneading is continuously performed (second kneading step).
2. After melt-kneading the whole amount of the component (a) contained in the resin composition of the present embodiment (first kneading step) and once cooling and pelletizing, the whole amount of the other components (b) to (d) is supplied and melted. Kneading is performed (second kneading step), a manufacturing method.
3. A method of melt-kneading all the components (a) to (d) contained in the resin composition of the present embodiment.

In particular, the polyphenylene ether or polyphenylene sulfide, which is the raw material of the component (a), the metallic silicon powder of the component (b), and the flake graphite of the component (c) are powdery, and the component (d) may be liquid. Therefore, it is difficult to bite into the extruder, and it is difficult to increase the production amount per hour. Furthermore, since the residence time of the resin in the extruder becomes long, heat deterioration easily occurs. From the above, the resin composition obtained by the above production method 1 or 2 is superior in the miscibility of each component as compared with the resin composition obtained by the production method 3 and the generation of crosslinked products and carbides due to heat deterioration. Is more preferable because the resin composition can be reduced and the production amount of the resin per hour can be increased, and a resin composition having excellent productivity and quality can be obtained.

Here, "the kneaded material is in a molten state in the first kneading step to the second kneading step" does not include a mode in which the component (a) is once melted, pelletized, and then melted again.

〔Molding〕
The molded article of the resin composition of the present embodiment is an optical device mechanical part, a part around a light source lamp, a sheet or film for a metal film laminated substrate, a hard disk internal part, an optical fiber connector ferrule, a printer part, a copy machine part, an automobile radiator tank. It can be widely used as molded parts such as automobile engine room parts and automobile lamp parts.

Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited thereto.
In addition, Example 16 is described as a reference example.

The methods for measuring physical properties used in Examples and Comparative Examples are shown below.
((1) Thermal conductivity)
The measurement was carried out by the hot wire method according to the method described in JIS R2616. The larger the value of thermal conductivity, the better the thermal conductivity.

((2) Resistivity and resistance value)
By the method described in JIS K6911, using Hiresta UP and Lorester GP (manufactured by Mitsubishi Chemical Co., Ltd.), the surface resistance and the volume resistance of five samples were measured under the conditions of a voltage of 100 V and a measurement time of 10 seconds, The average was taken as the surface resistance value (Rs) and the volume resistance value (Rv). Further, the surface resistance value (Rs) is multiplied by an electrode correction coefficient of the electrode used for measuring the surface resistance value (Rs): 30 to obtain a surface resistivity (Ω/sq.) (surface resistivity=surface resistance value). X electrode correction factor) was calculated.
Further, from the surface resistance value (Rs) and the volume resistance value (Rv) obtained by measuring the anisotropy of resistance value (surface resistance value/volume resistance value) by the above-described measuring method, the anisotropic value of the resistance value is calculated by the following formula. I asked for sex.
Anisotropy of resistance=(Rs)/(Rv)

((3) Warp)
The resin composition pellets obtained in Examples and Comparative Examples are supplied to a screw in-line type injection molding machine set at 240 to 310° C., and injection molding is performed at a mold temperature of 60 to 130° C. to obtain 150×. A flat plate of 150×2 mm was obtained.
Using the three-dimensional measuring machine (manufactured by Mitutoyo Co., Ltd.), a virtual plane is set by the least square method from the 15 points (A to O) shown in FIG. 1 for the flat plate, and the Z from the plane is set for 15 points. The deviation of the axial position was determined, and the value obtained by subtracting the minimum value from the maximum value was taken as the flatness of the flat plate. The smaller this value, the less the warp of the molded piece and the better the dimensional accuracy.

((4) Flame retardance (UL-94))
The test was carried out according to the vertical combustion test method of UL94 (standard defined by Under Writers Laboratories Inc., USA).

Raw materials used in Examples and Comparative Examples are shown below.
<(a) component: polyphenylene ether resin>
(A1): PPE (polyphenylene ether)/HIPS (high impact polystyrene) polymer alloy was obtained by the following method.
Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol (reduced viscosity measured at 30° C. with a chloroform solution having a concentration of 0.5 g/dL: 0.42 dL/g) 60% by mass, high-impact polystyrene (trade name “ H9405", PS Japan Co., Ltd., with a blending ratio of 40% by mass, a twin-screw extruder with a vent port set at 270 to 310°C (trade name "ZSK-40", COPERION WERNER & PFLEIDERER, Germany). Using a screw rotation speed of 250 rpm, polyphenylene ether and high-impact polystyrene are supplied from the first raw material supply port, melt-kneaded, and degassed under reduced pressure from the first vent port, and further depressurized through the second vent port. To obtain polymer alloy pellets. The PPE/HIPS polymer alloy obtained here was designated as (a1).

(A2): A PPS/PPE polymer alloy in which the matrix is polyphenylene sulfide and the dispersed particles have the morphology of polyphenylene ether was obtained by the following method.
Melt viscosity (value measured using a flow tester after holding at 300° C., load 196N, L/D=10/1 for 6 minutes) is 500 poise, extraction amount with methylene chloride is 0.4% by weight, -SX 67 mass% of linear type PPS having a repeating unit of p-phenylene sulfide having a base amount of 29 μmol/g, polyphenylene ether (reduced viscosity measured at 30° C. with a chloroform solution having a concentration of 0.5 g/dL: 0.42 dL/ g) 30% by mass, styrene-glycidylmethacrylate copolymer containing 5% by mass of glycidylmethacrylate (weight average molecular weight 110,000) 3% by mass of the compounding ratio, and a twin-screw extruder with a vent port set to 300°C ( Using the product name "ZSK-40", COPERION WERNER & PFLEIDER, Germany), polyphenylene ether, polyphenylene sulfide, styrene-glycidyl methacrylate copolymer is supplied from the first raw material supply port under the condition of screw rotation speed of 300 rpm. Then, melt kneading and degassing under reduced pressure from the first vent port, and further depressurizing degassing through a second vent port provided near the exit of the extruder were carried out to obtain polymer alloy pellets. The PPS/PPE polymer alloy obtained here was designated as (a2).

(A3): A polypropylene/PPPE polymer alloy having a morphology in which the matrix was polypropylene, the dispersed particles were polyphenylene ether, and the outer shell of the polyphenylene ether dispersed particles was coated with a hydrogenated block copolymer was obtained by the following method.
55% by mass of polypropylene (trade name "Novatech (registered trademark) PP MA3H", manufactured by Nippon Polypro Co., Ltd.), polyphenylene ether (reduced viscosity measured at 30° C. with a chloroform solution having a concentration of 0.5 g/dL: 0.42 dL/g 35% by mass, hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene amount 45%, number average molecular weight 86,000, molecular weight distribution 1.07, before hydrogenation A twin-screw extruder with a vent port set to 300°C with a blending ratio of 10% by mass of 1,2-vinyl bond amount of polybutadiene of 75%) (trade name "ZSK-40", COPERION WERNER & PFLEIDERER, Germany). Under a condition of screw rotation speed of 300 rpm, polyphenylene ether, hydrogenated block copolymer and a part (10% by mass) of polypropylene are supplied from the first raw material supply port to melt-knead and depressurize from the first vent port. After deaeration, the rest (45% by mass) of polypropylene was supplied from the second raw material supply port, melted and kneaded, and further deaerated under reduced pressure from the second vent port to obtain polymer alloy pellets. The PP/PPE polymer alloy obtained here was designated as (a3).

(A4): PA/PPE polymer alloy showing a morphology in which the matrix is polyamide (nylon 6), the dispersed particles are polyphenylene ether, and the hydrogenated block copolymer is dispersed in the polyphenylene ether dispersed particles are obtained by the following method. It was
Polyamide 6 (trade name "UBE Nylon (registered trademark) 1013B", manufactured by Ube Industries, Ltd.) 60% by mass, polyphenylene ether (reduced viscosity measured at 30°C with a chloroform solution having a concentration of 0.5 g/dL: 0.42 dL/ g) 32.7% by mass, a hydrogenated block copolymer (trade name "Clayton (registered trademark) G-1651", manufactured by Kraton Polymer Co., Ltd.) at 7% by mass, and maleic anhydride 0.3% by mass at a mixing ratio of: Using a twin-screw extruder with a vent port set to 300°C (trade name "ZSK-40", manufactured by COPERION WERNER & PFLEIDER, Germany) under the condition of screw rotation speed 300 rpm, polyphenylene ether from the first raw material supply port, Maleic anhydride and hydrogenated block copolymer are supplied to melt knead and degassed under reduced pressure from the first vent port, and polyamide (nylon 6) is further supplied from the second raw material supply port to melt and knead. Degassed under reduced pressure from the vent to obtain polymer alloy pellets. The PA/PPE polymer alloy obtained here was designated as (a4).

(A5): A polyester/PPE polymer alloy showing a morphology in which the matrix is polybutylene terephthalate and the dispersed particles are polyphenylene ether was obtained by the following method.
60% by mass of polybutylene terephthalate (trade name "Duranex (registered trademark) 2002", manufactured by Polyplastics Co., Ltd.), polyphenylene ether (reduced viscosity measured at 30° C. with a chloroform solution having a concentration of 0.5 g/dL: 0.42 dL /G) 38% by mass, styrene-glycidyl methacrylate copolymer containing 5% by mass of glycidyl methacrylate (weight average molecular weight 110,000) 2% by mass, and a twin screw extruder with a vent port set to 300°C. (Trade name "ZSK-40", manufactured by COPERION WERNER & PFLEIDER, Germany) under the condition of a screw rotation speed of 300 rpm, polyphenylene ether, polybutylene terephthalate and styrene-glycidyl methacrylate copolymer are supplied from the first raw material supply port. The polymer alloy was supplied, melted and kneaded, and deaerated under reduced pressure from the first vent port, and further deaerated under reduced pressure from a second vent port provided near the exit of the extruder to obtain polymer alloy pellets. The PBT/PPE polymer alloy obtained here was designated as (a5).

(A6): High-impact polystyrene (trade name "polystyrene H9405", manufactured by PS Japan).

(A7): Hydrogenated block copolymer (trade name "Clayton (registered trademark) G-1651", manufactured by Kraton Polymer Co., Ltd.).

(A8): Melt viscosity (measured using a flow tester after holding at 300° C., load 196 N, L/D=10/1 for 6 minutes) was 500 poise, and the amount of extraction with methylene chloride was 0.4. % By weight, a linear type PPS having a repeating unit of p-phenylene sulfide having an amount of -SX group of 29 μmol/g (the same as the PPS used for the component (a2)).

<(b) component: metallic silicon powder>
(B1): Metallic silicon powder having an average particle size of 18 μm (#200 manufactured by Kinsei Matec Co., Ltd.).
(B2): Metallic silicon powder having an average particle size of 15 μm (#350 manufactured by Kinsei Mathec Co., Ltd.).
(B3): Metallic silicon powder having an average particle size of 6 μm (#600 manufactured by Kinsei Matec Co., Ltd.).

<Flake graphite of component (c)>
(C1): Flake graphite having an average particle size of 400 μm (F#1 manufactured by Nippon Graphite Industry Co., Ltd.).
(C2): Flake graphite having an average particle size of 500 μm (F#585, manufactured by Nippon Graphite Industry Co., Ltd.).
(C3): Flake graphite having an average particle diameter of 130 μm (F#2, manufactured by Nippon Graphite Industry Co., Ltd.).
(C4): Flake graphite having an average particle size of 50 μm (F#3, manufactured by Nippon Graphite Industry Co., Ltd.).

<Condensed Phosphate Ester Flame Retardant as Component (d)>
(D1) Aromatic condensed phosphoric acid ester (trade name "CR-741", manufactured by Daihachi Chemical Industry Co., Ltd.)

<(e) Other ingredients>
(E1): Carbon fiber having an average fiber diameter of 6 μm (trade name “Pyrofil (registered trademark) TR066A”, manufactured by Mitsubishi Rayon Co., Ltd.)
(E2): Glass fiber having an average fiber diameter of 13 μm (trade name “ECS03T-249”, manufactured by Nippon Electric Glass Co., Ltd.).

[Examples 1 to 16], [Comparative examples 1 to 5]
The resin composition was manufactured using a twin-screw extruder ZSK-40 (manufactured by WERNER & PFLEIDER). In this twin-screw extruder, a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, and a first vacuum vent, a second raw material supply port, and a third raw material supply port are provided downstream thereof, and A second vacuum vent was provided downstream thereof. The second raw material supply port was provided from the opening at the top of the extruder using a gear pump.

Using the extruder set as described above, components (a1) to (a8) having the composition shown above are supplied from the first raw material supply port, components (d1) are supplied from the second raw material supply port, and (b1) to ((b1) to ( b3) component, (c1) to (c4) component, and (e1) to (e2) component are added from the third raw material supply port, the extrusion temperature is 240 to 310° C., the screw rotation speed is 300 rpm, and the discharge rate is 100 kg/hour. Melt kneading was performed under the conditions to produce pellets.
The pellets of this resin composition were fed to a screw in-line injection molding machine set to 250 to 310° C., and the mold temperature was 60 to 130° C. (80° C. when molding the PPE/HIPS polymer alloy-containing resin composition, 130° C. when molding a resin composition containing a PPS/PPE polymer alloy, 80° C. when molding a resin composition containing a PA/PPE polymer alloy, 60° C. when molding a resin composition containing a PP/PPE polymer alloy, PBT/ A plate-shaped molded product having a size of 75 mm×75 mm×thickness of 3 mm was obtained under the condition of 80° C. at the time of molding the resin composition containing the PPE polymer alloy. The plate-shaped molded product obtained here was allowed to stand at 23° C. and 50% relative humidity for 24 hours or more, and (1) thermal conductivity and (2) electrical resistivity were measured.
Further, a plate-shaped molded product of 150 mm×150 mm×thickness of 2 mm was produced under the same injection molding conditions as above, and (3) warpage was measured.
Further, a test piece having a length of 127 mm, a width of 12.7 mm and a thickness of 1.6 mm was molded under the same injection molding conditions as above. Using this, a vertical combustion test based on UL94 was performed, and (4) flame retardancy (UL94) was evaluated.
The results are also shown in Table 1. The mass% in the table is a value when the total amount of the resin composition is 100 mass %.
As shown in Table 1, it was found that the resin compositions of Examples 1 to 16 were excellent in thermal conductivity and non-insulating property, and also excellent in balance with warpage.

The molded product molded from the resin composition of the present invention has a high thermal conductivity and a surface resistivity of 1×10 ⁹ to 1×10 ¹⁴ Ω/sq. In the range of 1×10 ⁵ to 1×10 ⁹ Ω/sq. It is possible to provide a non-insulating resin molded product whose measured surface resistance value and volume resistance value are stable at an equivalent level in the static electricity diffusion range of It can be used as a conductive part of antistatic area and static electricity diffusion area in equipment and optical equipment. For example, chassis and cabinet such as digital versatile disk, optical equipment mechanical parts such as optical pickup slide base, light source lamp surrounding parts, metal film laminated substrate. Sheet or film, hard disk internal parts, optical fiber connector ferrule, laser beam printer internal parts (toner cartridge, etc.), inkjet printer internal parts, copy machine internal parts, automotive radiator room parts, automotive engine room parts, automotive lamp parts As such, it has industrial applicability.

Claims (13)

(A) 35 to 90% by mass of polyphenylene ether resin,
(B) 10 to 60 mass% of metallic silicon powder,
(C) 0 to 50 mass% of flake graphite,
(D) a condensed phosphoric acid ester-based flame retardant as an optional component,
Made (with the proviso that said component (a), the component (b), the component (c), and the total amount of the component (d) is 100 mass%),
The content of polyphenylene ether in the component (a) is 10 to 51.4 mass %,
A resin composition comprising: The resin composition according to claim 1, wherein the content of the polyphenylene ether in the resin composition is 10 to 40.5% by mass. Wherein component (a), a polyphenylene ether, a crystalline resin and at least one thermoplastic resin and the including selected from the group consisting of non-crystalline resin,請 Motomeko 1 or 2 resin composition according to. The crystalline resin is at least one selected from the group consisting of polyolefin, syndiotactic polystyrene, polyacetal, polyamide, polyester, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, and fluororesin,
The non-crystalline resin, atactic polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, polyamideimide, and it is at least one selected from the group consisting of polyetherimide resin of claim 3 Composition. The resin composition according to any one of claims 1 to 4 , wherein the component (b) is a metallic silicon powder having an average particle size of 8 to 25 µm. The resin composition according to any one of claims 1 to 5 , wherein the component (c) is flake graphite having an average particle diameter of 120 to 700 µm. Wherein (b) weight ratio of said the component (c) component ((b) mass of the mass / (c) of component) is 20/80 to 80/20, any one of claims 1 to 6 The resin composition according to item 1. 6 to 20% by mass of the condensed phosphate ester flame retardant (d) is contained with respect to a total of 100% by mass of the component (a), the component (b), the component (c) and the component (d). The resin composition according to any one of claims 1 to 7 . The resin composition according to any one of claims 1 to 8 , wherein the component (a) contains a polymer alloy of polyphenylene ether and atactic polystyrene. The resin composition according to any one of claims 1 to 8 , wherein the component (a) is a polymer alloy of polyphenylene ether and polyphenylene sulfide. Wherein component (a) is a polymer alloy of polyphenylene ether and a polyolefin resin composition according to any one of claims 1-8. Wherein component (a) is a polymer alloy of polyphenylene ether and polyamide resin composition according to any one of claims 1 to 8. Wherein component (a) is a polymer alloy of polyphenylene ether and polyester resin composition according to any one of claims 1-8.

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