JP6435604B2 - High heat dissipation thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition imparted with high thermal conductivity and a resin molded article molded from the composition.

  In recent years, in the fields of electrical / electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, etc. The request is coming out. Therefore, a high thermal conductive resin material was developed by mixing thermoplastic resin with high heat dissipation filler (filler) such as magnesium oxide, alumina (aluminum oxide), aluminum nitride, silicon nitride, boron nitride. (Patent Document 1).

  However, in order to sufficiently increase the thermal conductivity of the high thermal conductive resin material, it is necessary to add a large amount of filler, which causes a decrease in mechanical strength. On the other hand, as a method for improving the mechanical strength of the resin composition, a method of adding a fibrous reinforcing material is known (Patent Document 2). However, among the high heat dissipation fillers, alumina (aluminum oxide), aluminum nitride, silicon nitride, and the like are hard and hard, so when the resin composition is melt-kneaded, the fibrous reinforcing material is sheared, and as a result the mechanical strength of the resin composition There was a problem of reducing the strength.

JP 2002-256147 A JP 2010-53350 A

  Therefore, the problem to be solved by the present invention is that a thermoplastic resin molded body to which high heat conductivity is given by mixing a high hardness and high heat dissipation filler is excellent in mechanical strength even if a fibrous reinforcing material is added. Another object of the present invention is to provide a thermoplastic resin molded article, a thermoplastic resin composition capable of molding the molded article, and a method for producing the same.

  As a result of various studies, the inventors of the present application have found that a thermoplastic resin (A), a high heat dissipation filler (B) having a Mohs hardness of 5 or more, a high heat dissipation filler (C) having a Mohs hardness of less than 5, and Mohs A clay mineral (D) having a hardness of 2 or less, a fibrous reinforcing material (E), and metal silicon (F) are essential components, and these are mixed at a high speed when melt-kneaded so that a high-hardness filler (B) and When the low hardness clay mineral (D) is collided with a strong force to break down the agglomeration soul of the low hardness clay mineral (D), the thermal conductivity is improved while suppressing the decrease in mechanical strength. As a result, the present invention has been completed.

That is, the present invention relates to a thermoplastic resin (A), a high heat dissipation filler (B) having a Mohs hardness of 5 or more, a high heat dissipation filler (C) having a Mohs hardness of less than 5, and a clay mineral having a Mohs hardness of 2 or less. (D), a fibrous reinforcing material (E), and a high heat dissipation thermoplastic resin composition comprising metal silicon (F) as essential components,
The thermoplastic resin (A) is in the range of 20 to 75% by mass, and the total of the high heat dissipation filler (B), the high heat dissipation filler (C) and the clay mineral (D) is 10 to 50% by mass. The fibrous reinforcing material (E) is in the range of 10 to 40% by mass, the metal silicon (F) is in the range of 5 to 15% by mass, and
Using the thermoplastic resin as a matrix, the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), the fibrous reinforcing material (E), and metal silicon (F) Are dispersed and the average particle size of the clay mineral (D) is in the range of 8 μm or less, and a molded body formed by molding the composition.

  The present invention also relates to a thermoplastic resin (A), a high heat dissipation filler (B) having a Mohs hardness of 5 or more, a high heat dissipation filler (C) having a Mohs hardness of less than 5, and a clay mineral having a Mohs hardness of 2 or less. (D), fibrous reinforcing material (E), and metal silicon (F) are charged into a twin-screw kneading extruder, and the discharge amount (kg / hr) of the resin component and the screw rotation speed (rpm) The present invention relates to a method for producing a highly heat-dissipating thermoplastic resin composition, which is melt-kneaded under a kneading condition of a ratio (discharge amount / screw rotation number) of 0.02 to 2 (kg / hr / rpm).

  According to the present invention, in a thermoplastic resin molded body that is provided with high thermal conductivity by mixing a high-hardness heat-dissipating filler, even if a fibrous reinforcing material is added, thermoplastic resin molding having excellent mechanical strength Body, a thermoplastic resin composition capable of molding the molded body, and a method for producing the same.

The present invention relates to a thermoplastic resin (A), a high heat dissipation filler (B) having a Mohs hardness of 5 or more, a high heat dissipation filler (C) having a Mohs hardness of less than 5, and a clay mineral having a Mohs hardness of 2 or less (D ), A fibrous reinforcing material (E) and metal silicon (F) as essential components,
The thermoplastic resin (A) is in the range of 20 to 75% by mass, and the total of the high heat dissipation filler (B), the high heat dissipation filler (C) and the clay mineral (D) is 10 to 50% by mass. The fibrous reinforcing material (E) is in the range of 10 to 40% by mass, the metal silicon (F) is in the range of 5 to 15% by mass, and
Using the thermoplastic resin as a matrix, the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), the fibrous reinforcing material (E), and metal silicon (F) Are dispersed, and the clay mineral (D) has an average particle size of 8 μm or less.

  As the thermoplastic resin (A) used in the present invention, polyolefin, polystyrene, polyamide, vinyl halide resin, polyacetal, saturated polyester, polycarbonate, polyarylsulfone, polyarylketone, polyarylene ether, polyarylene sulfide, polyarylether Thermoplastic resins such as ketone, polyethersulfone, polyarylene sulfide sulfone, polyarylate, liquid crystal polyester, fluororesin and the like can be mentioned, but a thermoplastic resin selected from such a group can be used alone, or two or more A thermoplastic resin can also be used in combination as a polymer alloy.

  Among these, the melting point is 170 ° C. or higher, preferably 170 to 390 ° C., because it has excellent electrical insulation and has heat resistance sufficient to cope with the increase in calorific value accompanying recent improvements in electrical output. A range of thermoplastic resins can be mentioned as preferred resins, specifically polyamides having an aliphatic skeleton such as polyamide 6 (6-nylon), polyamide 66 (6,6-nylon) or polyamide 12 (12-nylon) , Polyamides having an aromatic skeleton such as polyamide 6T (6T-nylon), polyamide 9T (9T-nylon), and the like having a melting point of 170 ° C. or higher, preferably 170 to 310 ° C., polybutylene terephthalate, polyisobutylene Fusion of terephthalate, polyethylene terephthalate or polycyclohexene terephthalate Typical is a polyester resin having a point of 220 ° C. or higher, preferably 220 to 280 ° C., or a polyphenylene sulfide having a melting point of 265 ° C. or higher, preferably 265 to 350 ° C., more preferably 280 to 300 ° C. Polyarylene sulfide, polyether ether ketone having a melting point in the range of 300 to 390 ° C., melting point having parahydroxybenzoic acid in the skeleton is 300 ° C. or higher, preferably 300 ° C. to thermal decomposition temperature (380 ° C.) So-called general-purpose engineering plastics or super engineering, such as a liquid crystal polymer having a melting point of 220 ° C. or higher, or a thermoplastic resin having a melting point of 170 to 390 ° C. such as syndiotactic polystyrene having a melting point of 220 to 280 ° C. Plastic, Of preferably polyarylene sulfide having excellent flame retardancy and dimensional stability.

  The polyarylene sulfide resin (A1) preferably used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyarylene sulfide resin (A1) is represented by the following formula (1):

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）で表される構造部位を繰り返し単位とする樹脂である。

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). It is a resin having a structural site as a repeating unit.

Here, in the structural part represented by the formula (1), it is particularly preferable that R ¹ and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin (A1). In this case, those bonded at the para position represented by the following formula (2) and those bonded at the meta position represented by the following formula (3) are exemplified.

これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記構造式（２）で表されるパラ位で結合した構造であることが前記ポリアリーレンスルフィド樹脂（Ａ）の耐熱性や結晶性の面で好ましい。

Among these, the heat resistance of the polyarylene sulfide resin (A) is that the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2). It is preferable in terms of crystallinity.

  In addition, the polyarylene sulfide resin (A1) includes not only the structural portion represented by the formula (1) but also the following structural formulas (4) to (7).

で表される構造部位を、前記式（１）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本発明では上記式（４）〜（７）で表される構造部位は１０モル％以下であることが、ポリアリーレンスルフィド樹脂（Ａ１）の耐熱性、機械的強度の点から好ましい。前記ポリアリーレンスルフィド樹脂（Ａ１）中に、上記式（４）〜（７）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。

The structural site represented by the formula (1) may be included at 30 mol% or less of the total with the structural site represented by the formula (1). In particular, in the present invention, the structural site represented by the above formulas (4) to (7) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin (A1). When the polyarylene sulfide resin (A1) includes a structural moiety represented by the above formulas (4) to (7), the bonding mode thereof may be either a random copolymer or a block copolymer. May be.

  The polyarylene sulfide resin (A1) has the following formula (8) in its molecular structure.

で表される３官能性の構造部位、或いは、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以下であることが好ましい。

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly 1 mol%, based on the total number of moles with other structural sites. The following is preferable.

  The polyarylene sulfide resin (A1) preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1,000 [Pa · s], and further has a good balance between fluidity and mechanical strength. Therefore, the range of 5 to 100 [Pa · s] is preferable. However, melt viscosity (V6) measured at 300 ° C. is an orifice having a temperature / 300 ° C., a load of 1.96 MPa, an orifice length and an orifice diameter of 10/1 using a flow tester. Represents the melt viscosity after holding for 6 minutes. The PAS resin (A1) preferably has a non-Newtonian index in the range of 0.90 to 2.00. When the linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.20, more preferably in the range of 0.95 to 1.15, particularly 0.95 to 1.10. It is preferable that Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.

［ただし、ＳＲは剪断速度（秒^−１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］Ｎ値は１に近いほどポリアリーレンスルフィド樹脂は線状に近い構造であり、Ｎ値が高いほど分岐が進んだ構造であることを示す。

[Wherein SR represents a shear rate (second ⁻¹ ), SS represents a shear stress (dyne / cm ² ), and K represents a constant. The closer the N value is to 1, the closer the polyarylene sulfide resin is to a linear structure, and the higher the N value, the more branched the structure is.

  The production method of the polyarylene sulfide resin (A1) is not particularly limited. For example, 1) a method of polymerizing a dihalogenoaromatic compound and, if necessary, other copolymerization components in the presence of sulfur and sodium carbonate. 2) Self-condensation of p-chlorothiophenol with other copolymerization components if necessary, 3) In an organic polar solvent, sulfidizing agent and dihalogenoaromatic compound, and further if necessary Examples thereof include a method of reacting a copolymerization component, and 4) a method of melt polymerization of a diiodo aromatic compound, elemental sulfur and, if necessary, a polymerization inhibitor in the presence of a polymerization catalyst. Among these methods, the method 3) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 3), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound and A method for producing a polyarylene sulfide resin by reacting with a sulfidizing agent and controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent ( Japanese Patent Application Laid-Open No. 07-228699), a polyhaloaromatic compound, an alkali metal hydrosulfide and an organic acid alkali metal salt in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. 0.01-0.9 mol of organic acid alkali metal salt and 1 mol of water in the reaction system with respect to 1 mol of aprotic polar organic solvent A method of reacting while controlling the .02 mols (WO2010 / 058 713 pamphlet reference.) Is what is particularly preferably obtained by.

  The content of the thermoplastic resin (A) includes the thermoplastic resin (A), the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), and the fibrous reinforcing material (E). And the range of 20 to 75% by mass, more preferably 30 to 60% by mass with respect to the total of metal silicon (F).

The high heat dissipation filler (B) having a Mohs hardness of 5 or more used in the present invention has a Mohs hardness of 5 or more. In addition to the Mohs hardness, the thermal conductivity is preferably in the range of 20 or more [W / m · K]. Examples of such a high heat dissipation filler (B) include aluminum oxide, beryllium oxide, magnesium oxide, aluminum nitride, silicon nitride, silicon carbide, and the like, and these can be blended alone or in combination of two or more. In the present invention, alumina is preferable from the viewpoint of chemical stability of the material and cost.
The shape of the highly heat-dissipating filler (B) is not particularly limited, such as a spherical shape, a plate shape, or a round shape. However, the use of a spherical shape reduces wear on the cylinder surface of an extruder or injection molding machine or in the mold. Since it can reduce, it is preferable. When a spherical material is used as the high heat dissipating filler (B), its particle size is not particularly limited, but it is preferable to use a material having a 50% particle size on the basis of volume distribution and in the range of 1 to 100 [μm].

  The blending ratio of the high heat dissipation filler (B) is 16.6 with respect to the total of the high heat dissipation filler (B), the high heat dissipation filler (C), and the clay mineral (D) in the resin composition. It is preferably in the range of ˜72.2% by mass, more preferably in the range of 60 to 66.6% by mass. When the blending ratio of the high heat dissipating filler (B) in the resin composition is less than the range, the heat dissipation tends to be low, and when the blending ratio is greater than the range, the resin, the fibrous reinforcement, etc. The amount of the component is reduced, the mechanical strength of the composition is lowered, and the fluidity tends to be lowered.

  As the high heat dissipation filler (C) having a Mohs hardness of less than 5 used in the present invention, the Mohs hardness is less than 5. In addition to the Mohs hardness, the thermal conductivity is preferably in the range of 20 or more [W / m · K]. Examples of such a high heat dissipating filler (C) include boron nitride, zinc oxide and the like, and these can be blended singly or in combination of two or more. In the present invention, boron nitride is preferable from the viewpoint of chemical stability of the material and thermal conductivity.

  The shape of the highly heat-dissipating filler (C) is not particularly limited, such as a spherical shape, a plate shape, or a round shape, but it is preferable to use a plate shape because the thermal conductivity is further improved. When using a spherical thing as a high heat dissipation filler (C), the particle size does not have a restriction | limiting in particular, However, It is preferable to use the thing of the range of 1-100 [micrometers] with the 50% particle size of a volume distribution standard.

  The mixing ratio of the high heat dissipation filler (C) is 6.25 with respect to the total of the high heat dissipation filler (B), the high heat dissipation filler (C), and the clay mineral (D) in the resin composition. It is preferably in the range of ˜50 mass%, more preferably in the range of 12.5 to 25 mass%. When the blending ratio of the high heat dissipating filler (C) in the resin composition is less than the above range, the heat dissipation becomes fine, and when the blending ratio is greater than the above range, the resin, the fibrous reinforcement, etc. The amount of the component is reduced, the mechanical strength of the composition is lowered, and the fluidity tends to be lowered.

  The clay mineral (D) having a Mohs hardness of 2 or less used in the present invention preferably has a Mohs hardness of 2 or less, more preferably less than 2. Further, in addition to the Mohs hardness, it is preferable that the thermal conductivity is in the range of 1 to 5 [W / m · K]. Such clay minerals include talc, kaolinite, dickite, nacrite, hallosite, antigorite, monoclinic chrysotile stone, Kaolinites such as orthochrysotile, parachrysotile, lizardite, amesite, kellyite, berthierine, greena and nepouite (Koryo stone). Such clay minerals may have variations in Mohs hardness depending on the production area and composition, so it is more preferable to mix those having a Mohs hardness of 2 or less, more preferably less than 2 alone or in combination of two or more. preferable. In the present invention, talc is preferable from the viewpoint of the balance between hardness and thermal conductivity.

  Although there is no restriction | limiting in particular as a shape of this clay mineral (D), It is preferable from a point with which the contact probability between fillers increases using a plate-shaped thing, more specifically the thing of aspect ratio 10 or more. Moreover, when using a plate-shaped thing as a clay mineral, the particle size does not have a restriction | limiting in particular, However, It is preferable to use the thing of the range of 5-50 [micrometers] with the 50% particle size of a volume distribution standard.

  The blending ratio of the clay mineral (D) is 12.5 to the total of the high heat dissipating filler (B), the high heat dissipating filler (C) and the clay mineral (D) in the resin composition. The range is preferably 68.75% by mass, more preferably 12.5 to 37.5% by mass. If the blending ratio of the clay mineral (D) in the resin composition is less than the above range, the mechanical strength of the composition tends to decrease. The amount of other components such as materials decreases, and the mechanical strength of the composition tends to decrease.

  In the resin composition of the present invention, the total blending ratio of the high heat dissipation filler (B), the high heat dissipation filler (C), and the clay mineral (D) is a high heat dissipation filler having a Mohs hardness of 5 or more. The range of 10-50 mass% with respect to the sum total of (B), the high heat dissipation filler (C) whose Mohs hardness is less than 5, Mohs hardness 2 or less clay mineral (D), and fibrous reinforcement (E) It is preferable that it is in the range of 30 to 40% by mass. The total blending ratio of the high heat dissipating filler (B), the high heat dissipating filler (C) and the clay mineral (D) in the resin composition is within the above range, and the moldability, mechanical strength and heat conduction are within the above ranges. It is preferable because of good properties.

  Examples of the fibrous reinforcing material (E) used in the present invention include inorganic fibrous reinforcing materials such as glass fibers and basalt fibers, aramid fibers, nylon MXD6 fibers (from a co-condensation polymer of m-xylylenediamine and adipic acid. Organic fiber reinforcing materials such as PET fibers, PBT fibers, and the like, and these may be used alone or in combination of two or more. In the present invention, glass fiber is preferable from the viewpoint of maintaining insulation as the resin composition.

  Although there is no restriction | limiting in particular as a fiber diameter and fiber length of a fibrous reinforcement (E), From a viewpoint of a filling rate and mechanical strength, a thing with the fiber diameter of the range of 5-15 [micrometers] is preferable, and fiber The thing whose length is the range of 1-5 [mm] is preferable.

  The blending ratio of the fibrous reinforcing material (E) is as follows: the thermoplastic resin (A), the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), and the fibrous reinforcement (E ) And metal silicon (F) in a range of 10 to 40% by mass, and more preferably in a range of 20 to 30% by mass. When the blending ratio of the fibrous reinforcing material (E) in the resin composition is less than the range, the mechanical strength tends to be low, and when the blending ratio is more than the range, the resin and the high heat dissipation filler are relatively used. The amount of other components decreases, and the mechanical strength and thermal conductivity of the composition tend to decrease.

  As the metal silicon (F) used in the present invention, a known polycrystal composed of silicon atoms can be used as long as the effects of the present invention are not impaired. The shape of the metal silicon is not particularly limited. For example, a powdery powder such as dendritic powder, flake powder, square powder, spherical powder, granular powder, acicular powder, amorphous powder, and spongy powder is preferable. As mentioned. Moreover, the mixture of these shapes may be sufficient. The metal silicon production method may be a conventionally known method, and examples thereof include an electrolytic method, a mechanical pulverization method, an atomization method, a heat treatment method, a chemical production method, and the like, and are not limited to these production methods. The silicon content in the metal silicon is not particularly limited, and is preferably a resin composition having particularly excellent thermal conductivity. Therefore, the silicon content is preferably in the range of 99% by mass or less, and 98% by mass. % Or less is more preferable, particularly 94% or less is more preferable. On the other hand, the lower limit of the silicon content is not particularly limited, but is preferably in the range of 80% by mass or more, more preferably in the range of 85% by mass or more, and particularly preferably in the range of 90% by mass or more. In addition, since the metal silicon becomes a thermoplastic resin composition excellent in mechanical properties and thermal conductivity, it is preferable that the average particle diameter (D50) measured by a laser diffraction scattering method is 1 μm or more. As such silicon metal, various grades are commercially available from Kinsei Tech Co., Ltd. depending on the Si content and particle size, and these can be used.

  The blending ratio of the metal silicon (F) is the thermoplastic resin (A), the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), and the fibrous reinforcement (E). And 5 to 15% by mass, more preferably 7 to 10% by mass, based on the total of metal silicon (F).

  If necessary, the thermoplastic resin composition of the present invention may be blended with an impact resistance imparting agent (G). Examples of the impact resistance imparting agent include the thermoplastic elastomer obtained by copolymerizing an α-olefin and a vinyl polymerizable compound. Examples of the α-olefins include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compound include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid, and other carbons. Examples thereof include unsaturated dicarboxylic acids having 4 to 10 atoms, mono- and diesters thereof, α, β-unsaturated dicarboxylic acids such as acid anhydrides and derivatives thereof, glycidyl (meth) acrylate, and the like.

  In addition, since there exists a tendency for an elongation characteristic to fall when there are too many compounding quantities of an impact resistance imparting agent (G), it is preferable that it is 5 mass% or less in a thermoplastic resin composition, and is 1 mass% or less. More preferably.

  In addition, other known and commonly used release agents, colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant aids, rust inhibitors, etc. Additives can be appropriately blended.

  The method for producing the highly heat-dissipating thermoplastic resin composition described in detail above specifically includes a thermoplastic resin (A), a high heat dissipating filler (B) having a Mohs hardness of 5 or more, and a Mohs hardness of less than 5. High heat dissipating filler (C), clay mineral (D) with a Mohs hardness of 2 or less, fibrous reinforcing material (E), metal silicon (F), and other compounding ingredients as necessary, as described above A method of uniformly mixing with a tumbler or a Henschel mixer so as to achieve the composition ratio, then charging the mixture into a twin screw extruder and melt-kneading can be mentioned. By producing under such conditions, the thermoplastic resin (A) is used as a matrix, the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), and the fibrous reinforcement. The material (E) and the metal silicon (F) can be uniformly dispersed.

  The above production method will be described in more detail. Each of the above-described components is put into a twin-screw extruder, and the melting point of the thermoplastic resin (A) is higher than the melting point, preferably the melting point + 10 ° C. or higher, more preferably the melting point + 10. There is a method of melt kneading in a temperature range of from ° C to melting point + 100 ° C, more preferably in a temperature range of melting point + 20 ° C to melting point + 50 ° C, specifically at a set temperature of about 190 to 400 ° C.

  In the melt-kneading, the ratio (discharge amount / screw rotation number) between the discharge amount (kg / hr) of the blended component and the screw rotation speed (rpm) is 0.02 to 2 (kg / hr / rpm). It is preferable to carry out under conditions. Generally, a high heat dissipation material has a high content of the fibrous reinforcing material (E) and a high-hardness filler component, and excessive torque is applied. / Screw speed) is also low. However, in the present invention, the thermoplastic resin is contained by setting the ratio (discharge amount / screw rotation number) higher than usual while containing the fibrous reinforcing material (E) and the high-hardness filler component. A high heat dissipating filler (B), a high heat dissipating filler (C), a clay mineral (D), the fibrous reinforcing material (E), and metal silicon (F) are dispersed as a matrix, and a clay mineral ( The average particle size of D) is finely dispersed so as to be in the range of 8 μm or less, and the formation of such a morphology improves the thermal conductivity.

  Therefore, the high heat-dissipating thermoplastic resin composition of the present invention has a ratio (discharge amount / screw rotation number) between the discharge amount (kg / hr) of the blended component and the screw rotation speed (rpm) from the above viewpoint. It is preferable to set in the range of 02 to 2 (kg / hr / rpm), more preferably 0.05 to 0.8 (kg / hr / rpm), and further 0.07 to 0.2 ( kg / hr / rpm) is particularly preferable.

  In the resin composition of the present invention, the dispersibility of (B) to (F) is improved by the above production method, and the agglomeration soul of the clay mineral (D) is crushed, and the average of the clay mineral (D) The particle size is in the range of 8 μm or less. However, the average particle size referred to in the present invention means that the cross section of the resin composition (for example, pellet) is observed with a scanning electron microscope (SEM), and the major axis of a plurality of dispersed clay minerals (D) is randomly selected. It means the number average particle diameter selected, measured and averaged. The lower limit value of the average particle diameter of the clay mineral (D) in the composition after melt-kneading is a case where it is finely dispersed below the detection limit when the cross section of the composition is observed with a scanning electron microscope (SEM). However, since heat conductivity becomes favorable, the range of 1-8 micrometers is preferable, and the thing of 3-6 micrometers is more preferable.

  In addition, the fibrous reinforcing material (E) among the blended components is introduced into the extruder from the side feeder of the twin-screw extruder because the dispersibility of the fibrous reinforcing material (E) becomes good. preferable. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging portion to the side feeder with respect to the total screw length of the twin-screw extruder is in the range of 0.1 to 0.6. In particular, the range of 0.2 to 0.4 is particularly preferable.

  Usually, although the said high heat dissipation filler (B) provides the outstanding heat conductivity, since the material is hard, it exists in the tendency which shears a fiber reinforcement (E) and eventually reduces mechanical strength. For this reason, in the present invention, by adding the clay mineral (D) having a Mohs hardness of 2 or less, the clay mineral (D) exerts a buffering action, so that the fiber reinforcement by the high heat dissipation filler (B) is performed. It is considered that it is possible to prevent shearing of the material (C) and suppress a decrease in mechanical strength.

  Furthermore, the resin molded body of the present invention can be formed by a known molding method such as injection molding, extrusion molding or injection compression molding of the resin composition.

  Since the molded product obtained by molding the highly heat-dissipating thermoplastic resin composition of the present invention is excellent in thermal conductivity and mechanical strength, heat generated inside such as heat exchangers and heat sinks is radiated to the outside. For example, connectors, printed circuit boards, LEDs, sensors, sockets, terminal blocks, motor parts, ECU cases, optical pickups, lamp reflectors and sealing molded products, etc. Injection molding or compression molding of interior parts such as electrical parts, automobile parts, various buildings, aircraft and automobiles, precision parts such as OA equipment parts, camera parts and watch parts, or composites, sheets, pipes, etc. Widely useful as a material for various molding processes such as extrusion or pultrusion, or as a material for fibers or films That.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.

[Thermal conductivity]
In accordance with JIS-R2618 “Testing method for thermal conductivity of fireproof insulation bricks by the hot wire method”, after measuring the thermal conductivity of a 120 × 60 × 20 mm molded product combined with ISO D2, JIS-R1611 “Ceramics” In “Measurement of thermal diffusivity”, the measured value was converted and evaluated using a conversion formula with the case of measuring a 1 mmt molded product.

[Average remaining fiber length]
After obtaining ash in accordance with JIS-K7250-1 “Plastics—Method for determining ash content A method direct ashing method”, observing the ash content with a microscope, and measuring the length of 500 glass fibers at random, the average Values were calculated and evaluated.

[Bending strength]
Conforms to JIS-K7171 "Plastics-Testing method for bending properties". The test piece was cut into ISO D2 test standard dimensions, and the bending strength in the flow direction at 2 mmt was evaluated.

[Particle size]
The 50% particle size based on the volume distribution measured by a laser diffraction / scattering particle size distribution measuring device was measured.

[Melt viscosity of polyarylene sulfide resin (V6)]
Using a flow tester (Shimadzu Corporation Koka-type flow tester “CFT-500D type”), the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio is 10/1. The melt viscosity after holding for 6 minutes was measured using an orifice.

[Surface resistivity]
The surface resistivity of the ISO D2 test piece was measured at an applied voltage of 1000 V using Hiresta UP (manufactured by Mitsubishi Chemical Analytech).

[Volume resistivity]
The volume resistivity of the ISO D2 test piece was measured at an applied voltage of 1000 V using Hiresta UP (manufactured by Mitsubishi Chemical Analytech).

[Dielectric breakdown strength]
Conforms to JIS-C2110 “Solid Electrical Insulating Material-Test Method for Dielectric Breakdown Strength”. The test specimen was 100 × 100 × 2 mm, and the dielectric breakdown strength was measured at 23 ° C. with a boosting speed of 2 kV / sec, a spherical shape with an upper electrode of 20 mm, and a cylindrical shape with a lower electrode of 25 mm.

(Examples 1-8 / Reference Examples 1-4)
Polyarylene sulfide resin (A1) shown in Tables 1 to 3 below, a high heat dissipation filler (B) having a Mohs hardness of 5 or more, a high heat dissipation filler (C) having a Mohs hardness of less than 5, and a Mohs hardness of 2 or less The clay mineral (D), fibrous reinforcing material (E), metal silicon (F), and other blending components as necessary were uniformly mixed with a tumbler to obtain a blending material. Thereafter, the blended material was charged into a vented twin-screw extruder “TEX-30” manufactured by Nippon Steel Works, Ltd., resin component discharge rate 15 kg / hr, screw rotation speed 200 rpm, resin component discharge rate (kg / hr) And screw rotation speed (rpm) ratio (discharge amount / screw rotation speed) = 0.075 (kg / hr / rpm), maximum torque 40 (A), and melt kneading at a set resin temperature of 300 ° C. Pellets were obtained.

  In order to measure the thermal conductivity, bending strength, surface resistivity, volume resistivity, and dielectric breakdown strength of the molded product, a test piece was prepared and measured by injection molding. The results are shown in Tables 1-3. In addition, the unit in a table | surface is a mass part unless there is particular notice.

(Comparative Example 1)
Except that the metal silicon (F) was replaced with alumina (B1), a pellet of the resin composition was obtained in the same manner as in Example 1, a test piece was prepared by injection molding, and the thermal conductivity, bending strength, The surface resistivity, volume resistivity, and dielectric breakdown strength were measured.

(Comparative Example 2)
Except that the metallic silicon (F) was replaced with flaky graphite (F2), a pellet of the resin composition was obtained in the same manner as in Example 1, and a test piece was prepared by injection molding to obtain the thermal conductivity and bending strength of the molded product. The surface resistivity, volume resistivity, and dielectric breakdown strength were measured.

PPS (A1): Polyarylene sulfide resin manufactured by DIC Corporation (thermal conductivity 0.2 (W / m · K), V6 melt viscosity 15 [Pa · s]
PA (A2): Polyamide 6 resin (thermal conductivity 0.25 (W / m · K)) manufactured by Ube Industries, Ltd.
Alumina (B1): _{Spherical, D 50/7 (μm)} , Mohs hardness 9, the thermal conductivity of 25 (W / m · K)
Alumina (B2): _{Spherical, D 50/11 (μm)} , Mohs hardness 9, the thermal conductivity of 25 (W / m · K)
Boron nitride (C1): plate-like, D ₅₀ /25.6 (μm), Mohs hardness 2, thermal conductivity 60 (W / m · K)

Talc (D1): aspect ratio _{<20, D 50/20 (} μm), Mohs hardness 1, the thermal conductivity 3 (W / m · K)
Talc (D2): aspect _{ratio> 40, D 50/7 (} μm), Mohs hardness 1, the thermal conductivity 3 (W / m · K)
Talc (D3): aspect ratio _{<20, D 50/6 (} μm), Mohs hardness 1, the thermal conductivity 3 (W / m · K)
Kaolin _{(D4): D 50/5} (μm), Mohs hardness 2.5, thermal conductivity 1.5 (W / m · K)
Glass fiber (E1): fiber diameter / 10 (μm), fiber length / 3 (mm), thermal conductivity 1 (W / m · K)
Metal Si (F1): Metallic silicon “# 200” manufactured by Kinsei Matech Co., Ltd. (silicon content in metal silicon is 98.4% by mass, average particle diameter is 17 μm, irregularly shaped powder)
Graphite (F2): Scaled graphite “8094” (average particle size 250 μm) manufactured by Nishimura Graphite Co., Ltd.
Other additives (G1): ethylene / glycidyl methacrylate (88/12% by mass) copolymer

[Clay mineral particle size]
About the cross section of the resin pellet of Example 1 and Comparative Example 1, an element mapping image was obtained with an element peculiar to clay minerals using an SEM / EDS apparatus (“JSM-6360A” manufactured by JEOL Ltd.). Of the obtained element mapping images, about 30 points of the major axis were randomly selected, and the number average particle diameter was calculated. The number average particle size of the pellets of Example 1 was 5 μm, and the number average particle size of Comparative Example 1 was 10 μm.

Claims (8)

Thermoplastic resin (A), high heat dissipation filler (B) with Mohs hardness of 5 or more, high heat dissipation filler (C) with Mohs hardness of less than 5, clay mineral (D) with Mohs hardness of 2 or less and fibrous A highly heat-dissipating thermoplastic resin composition comprising reinforcing material (E) and metal silicon (F) as essential components,
The thermoplastic resin (A) is in the range of 20 to 75% by mass, and the total of the high heat dissipation filler (B), the high heat dissipation filler (C) and the clay mineral (D) is 10 to 50% by mass. The fibrous reinforcing material (E) is in the range of 10 to 40% by mass, the metal silicon (F) is in the range of 5 to 15% by mass, and
Using the thermoplastic resin as a matrix, the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), the fibrous reinforcing material (E), and metal silicon (F) And the clay mineral (D) has an average particle size of 8 μm or less. Before Kinetsu thermoplastic resin (A), claim 1 high heat radiation thermoplastic resin composition according melting point is more than 170 ° C..   The blending ratio of the clay mineral (D) is 12.5 with respect to the total of the high heat dissipating filler (B), the high heat dissipating filler (C) and the clay mineral (D) in the resin composition. The high heat dissipation thermoplastic resin composition of Claim 1 or 2 which is the range of -68.75 mass%.   The molded object formed by melt-molding the high heat dissipation thermoplastic resin composition as described in any one of Claims 1-3. Thermoplastic resin (A), high heat dissipation filler (B) with Mohs hardness of 5 or more, high heat dissipation filler (C) with Mohs hardness of less than 5, clay mineral (D) with Mohs hardness of 2 or less and fibrous Reinforcing material (E) and metallic silicon (F) are charged into a twin-screw kneading extruder and the ratio of the resin component discharge rate (kg / hr) to the screw rotation speed (rpm) (discharge rate / screw) Characterized by being melt-kneaded under kneading conditions in which the number of revolutions) is 0.02 to 2 (kg / hr / rpm),
The thermoplastic resin (A) is in the range of 20 to 75% by mass, and the total of the high heat dissipation filler (B), the high heat dissipation filler (C) and the clay mineral (D) is 10 to 50% by mass. The method for producing a highly heat-dissipating thermoplastic resin composition in which the fibrous reinforcing material (E) is in the range of 10 to 40% by mass and the metal silicon (F) is in the range of 5 to 15% by mass. .   The high heat dissipation thermoplastic resin composition comprises the thermoplastic resin as a matrix, the high heat dissipation filler (B), the high heat dissipation filler (C), the clay mineral (D), and the fibrous reinforcement. The method for producing a highly heat-dissipating thermoplastic resin composition according to claim 5, wherein the material (E) is dispersed and the particle size of the clay mineral (D) is in the range of 8 µm or less.   The method for producing a high heat dissipation thermoplastic resin composition according to claim 5 or 6, wherein the thermoplastic resin (A) has a melting point of 170 ° C or higher.   The blending ratio of the clay mineral (D) is 12.5 with respect to the total of the high heat dissipating filler (B), the high heat dissipating filler (C) and the clay mineral (D) in the resin composition. The manufacturing method of the high heat dissipation thermoplastic resin composition of any one of Claims 5-7 which is the range of -68.75 mass%.