JP6809083B2 - Polyarylene sulfide resin compositions, molded articles and methods for producing them - Google Patents

Description

The present invention relates to polyarylene sulfide resin compositions, molded articles, and methods for producing them.

In recent years, engineering plastics having excellent productivity and moldability and high heat resistance have been developed, and because of their light weight, they are widely used as materials for electric, electronic devices, automobiles, etc. as alternative materials to metal materials. In particular, polyphenylene sulfide (hereinafter, sometimes abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter, sometimes abbreviated as PPS) resin has excellent heat resistance, mechanical strength, and chemical resistance. It is also excellent in molding processability and dimensional stability, and is used as a material for electrical and electronic equipment parts, automobile parts, etc. by utilizing these characteristics.

In addition, in these fields such as electrical / electronic equipment parts and automobile parts materials, the amount of heat generated is increasing along with the increase in output, and further improvement of the thermal conductivity of the material itself is urgently needed to improve heat dissipation characteristics. It was an issue.

Therefore, a molded product having a molded product surface with a surface roughness Rz of 6 μm or less, which is made by blending boron nitride and a basic magnesium sulfate filler (inorganic short fibers with a fiber diameter of 0.5 to 1.0 μm) in PPS resin, is produced. It is known, and a method of improving heat dissipation characteristics by bringing the surface of the molded product into close contact with a heat radiation object is known (see, for example, Patent Document 1). However, since heat is conducted in the molded product along the direction of the filler oriented parallel to the surface of the molded product during injection molding, the heat conducted from the heat-dissipating object to the surface of the molded product is lateral to the surface of the molded product. It only conducts in the direction (surface direction), and the thermal conductivity in the thickness direction (depth direction) is insufficient with respect to the surface of the molded product, and not only is there room for improvement to improve the thermal conductivity, but also There was room for improvement in the mechanical strength in the TD direction (direction perpendicular to the resin flow direction during melt molding; the same applies hereinafter).

JP-A-2014-234407

Further, the problem to be solved by the present invention is to maintain the original characteristics of the polyarylene sulfide resin, and to obtain thermal conductivity in the thickness direction (depth direction) and mechanical strength in the TD direction with respect to the surface of the molded product. An object of the present invention is to provide an excellent molded product, a polyarylene sulfide resin composition capable of providing the molded product, and a method for producing the same.

As a result of diligent research to solve the above problems, the present inventors have made a polyarylene sulfide resin a whisker having a larger fiber diameter than the conventional one, that is, a single crystal having a needle-like structure and a spherical filler as essential components. The polyarylene sulfide resin composition obtained by melt-kneading has thermal conductivity in the thickness direction (depth direction) and the TD direction with respect to the surface of the molded product as well as the surface direction of the molded product (orientation direction of fillers such as whiskers). We have found that it is possible to produce a molded product having excellent mechanical strength, and have completed the present invention.

That is, the present invention contains a polyarylene sulfide resin (A), a whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm, and a spherical filler (C) having a number average particle diameter in the range of 5 to 40 μm as essential components. The present invention relates to a method for producing a polyarylene sulfide resin composition to be melt-kneaded.

Further, the present invention contains a polyarylene sulfide resin (A), a whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm, and a spherical filler (C) having a number average particle diameter in the range of 5 to 40 μm as essential components. The present invention relates to a polyarylene sulfide resin composition, which is characterized by the above.

Further, the present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition.

According to the present invention, a molded product having excellent thermal conductivity in the thickness direction (depth direction) and mechanical strength in the TD direction with respect to the surface of the molded product while maintaining the original characteristics of the polyarylene sulfide resin. It is possible to provide a polyarylene sulfide resin composition which can provide an article and a method for producing the same.

The method for producing the polyarylene sulfide resin composition of the present invention includes a polyarylene sulfide resin (A), a whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm, and a spherical filler having a number average particle diameter of 5 to 40 μm. It is characterized by melt-kneading with C) as an essential component.

The polyarylene sulfide resin, which is an essential component in the method for producing a polyarylene sulfide resin composition of the present invention, has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit, and is specific. The following general 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の範囲のアルキル基、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と、必要に応じてさらに下記一般式（２）

(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group in the range of 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, and an ethoxy group). The structural part to be formed and, if necessary, the following general formula (2)

で表される３官能性の構造部位と、を繰り返し単位とする樹脂である。式（２）で表される３官能性の構造部位は、他の構造部位との合計モル数に対して０．００１〜３モル％の範囲が好ましく、特に０．０１〜１モル％の範囲であることが好ましい。

It is a resin having a trifunctional structural part represented by (1) and a repeating unit. The trifunctional structural site represented by the formula (2) is preferably in the range of 0.001 to 3 mol%, particularly in the range of 0.01 to 1 mol%, based on the total number of moles with the other structural sites. Is preferable.

Here, the structural portion represented by the general formula (1) is preferably a hydrogen atom, particularly preferably R ¹ and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those that are combined at the para position represented by the following formula (3) and those that are combined at the meta position represented by the following formula (4) can be mentioned.

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一般式（３）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の耐熱性や結晶性の面で好ましい。

Among these, the heat resistance and crystallinity of the polyarylene sulfide resin is that the bond of the sulfur atom to the aromatic ring in the repeating unit has a structure in which the sulfur atom is bonded at the para position represented by the general formula (3). It is preferable in terms of surface.

Further, the polyarylene sulfide resin has not only the structural parts represented by the general formulas (1) and (2) but also the following structural formulas (5) to (8).

で表される構造部位を、前記一般式（１）と一般式（２）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一般式（５）〜（８）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中に、上記一般式（５）〜（８）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 portion represented by the above may be contained in an amount of 30 mol% or less of the total of the structural portion represented by the general formula (1) and the general formula (2). In particular, in the present invention, the structural portion represented by the general formulas (5) to (8) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains structural sites represented by the general formulas (5) to (8), the bonding mode thereof may be either a random copolymer or a block copolymer. Good.

Further, the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less, particularly 1 in terms of the total number of moles with other structural sites. It is preferably mol% or less.

The physical characteristics of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.

(Melting viscosity)
The polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa · s], and further improves the balance between fluidity and mechanical strength. Therefore, the range of 2 to 500 [Pa · s] is more preferable, and the range of 2 to 200 [Pa · s] is particularly preferable. In the present invention, the melt viscosity (V6) is measured by using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500C, at 300 ° C., a load of 1.96 × 10 ⁶ Pa, L / D = 10. The melt viscosity measured after holding for 6 minutes at 1/1 is used as the measured value.

(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.99 to 1.50, and more preferably in the range of 0.95 to 1.20. Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, in the present invention, the non-Newtonian index (N value) is the shear rate (SR) under the conditions of melting point + 20 ° C., ratio of orifice length (L) to orifice diameter (D), and L / D = 40 using a capillograph. ) And shear stress (SS) are measured and calculated using the following formula. The closer the non-Newtonian index (N value) is to 1, the more linear the structure is, and the higher the non-Newtonian index (N value) is, the more branched the structure is.

［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。］

[However, SR indicates the shear rate (sec- ¹ ), SS indicates the shear stress (Dyne / cm ² ), and K indicates a constant. ]

(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited, but for example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component. In addition, a method of polymerizing, 2) a method of adding a dihalogeno aromatic compound in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerizing component to polymerize, 3) Examples thereof include a method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is general and preferable. At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno aromatic compound is introduced in the organic polar solvent. And a sulfide agent are added as necessary to a polyhalogeno aromatic compound to cause a reaction, and the amount of water in the reaction system is adjusted to the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by control (see JP-A-07-2286999), or if necessary with a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotonic polar organic solvent. Polyhalogeno aromatic compounds or other copolymerization components are added to add alkali metal hydrosulfides and organic acid alkali metal salts to organic acid alkali metal salts in the range of 0.01 to 0.9 mol per 1 mol of sulfur source. It is particularly preferable to obtain one obtained by a method of reacting while controlling the amount of water in the reaction system to 0.02 mol or less with respect to 1 mol of the aprotonic polar organic solvent (see WO2010 / 058713 pamphlet). Specific examples of dihalogeno aromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide, and the above compounds. Examples of the compound having an alkyl group having an alkyl group in the range of 1 to 18 carbon atoms in the aromatic ring of are 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3 as polyhalogeno aromatic compounds. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.

The method for post-treating the reaction mixture containing the polyarylene sulfide resin obtained in the polymerization step is not particularly limited. For example, (1) after completion of the polymerization reaction, the reaction mixture is first used as it is, or an acid or a base. After adding the solvent, the solvent was distilled off under reduced pressure or normal pressure, and then the solid substance after the solvent was distilled off was water, a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, and methyl ethyl ketone. , Wash once or twice or more with a solvent such as alcohols, and further neutralize, wash with water, filter and dry, or (2) after completion of the polymerization reaction, add water, acetone, methyl ethyl ketone, alcohols, etc. to the reaction mixture. Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and at least poor for polyarylene sulfide) are used as precipitants. Addition to precipitate solid products such as polyarylene sulfide and inorganic salts, which are separated by filtration, washed and dried, or (3) after completion of the polymerization reaction, a reaction solvent (or low molecular weight) is added to the reaction mixture. An organic solvent having the same solubility as the polymer) is added and stirred, and then filtered to remove the low molecular weight polymer, and then washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc. Then, neutralization, washing with water, filtration and drying are performed. (4) After completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and if necessary, acid treatment with water at the time of washing with water. , (5) After completion of the polymerization reaction, the reaction mixture is filtered, washed once or twice or more with a reaction solvent, and further washed with water, filtered and dried, and the like. ..

In the post-treatment methods as illustrated in (1) to (5) above, the polyarylene sulfide resin may be dried in vacuum, in air, or in an atmosphere of an inert gas such as nitrogen. You may.

In the method for producing a polyarylene sulfide resin composition of the present invention, whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm (hereinafter, may be referred to as whiskers (B)) are blended as essential components. The whiskers (B) are single crystals having a needle-like structure.

The number average fiber diameter of the whiskers (B) used in the present invention is preferably in the range of 2 to 50 μm, more preferably in the range of 3 μm or more from the viewpoint of excellent thermal conductivity, and further 7 μm. Those in the above range are more preferable, while those in the range of 35 μm or less are preferable, and those in the range of 25 μm or less are more preferable from the viewpoint of excellent fluidity.

The aspect ratio (number average fiber length / number average fiber diameter) of the whiskers (B) is preferably in the range of 1.5 to 50, and more than 2 or more which are more excellent in thermal conductivity in the lateral direction of the surface of the molded product. The one in the range of 50 or less is preferable, and the one in the range of 10 or more is more preferable, while the one in the range of 50 or less is preferable and the one in the range of 30 or less is further preferable from the viewpoint of excellent mechanical strength, particularly the mechanical strength in the weld portion. Those in the range are more preferable, and those in the range of 20 or less are more preferable.

The number average fiber length of the whisker (B) is not particularly limited as long as it is within the range calculated from the number average fiber diameter and the aspect ratio, but is, for example, in the range of 5 to 800 μm. Is preferable, and those in the range of 30 to 300 μm are more preferable.

In the method for producing a polyarylene sulfide resin composition of the present invention, the blending ratio of the whisker (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A) from the viewpoint of excellent thermal conductivity. It is preferably in the range of 5 to 90 parts by mass, preferably in the range of 10 to 80 parts from the viewpoint of excellent fluidity and mechanical strength, particularly mechanical strength in the weld portion, in addition to thermal conductivity. It is more preferably in the range of parts by mass.

As the whiskers (B) used in the present invention, either commercially available products or synthetic products may be used, and the whiskers are not particularly limited. For example, wollastonite, zinc oxide whiskers, calcium carbonate whiskers, and oxidation. Examples thereof include titanium whiskers, magnesium sulfate whiskers, potassium titanate whiskers, aluminum borate whiskers, calcium silicate whiskers (zonotrite), silicon carbide whiskers, silicon nitride whiskers, alumina whiskers, graphite whiskers and the like. Among these, wollastonite, zinc oxide whiskers, calcium carbonate whiskers, titanium oxide whiskers, and magnesium sulfate whiskers are preferable because of their excellent thermal conductivity, mechanical strength, and fluidity. Last night is particularly preferred.

Commercially available products of Wollastonite include Tomoe Engineering Co., Ltd.'s "NYAD-G", the company's "NYAD-G", the company's "NYAD 400", the company's "NYAD 1250", the company's "NYGLOS 4W", and the company. "NYGLOS 8" manufactured by the same company, "NYGLOS 12" manufactured by the same company, "NYGLOS 20" manufactured by the same company, and the like can be used. Further, as the whisker-like inorganic filler (B), a filler whose surface is treated with a silane coupling agent may be used. As these silane coupling agents, those described later can be selected according to desired properties.

In the method for producing a polyarylene sulfide resin composition of the present invention, a spherical filler (C) having a number average particle diameter in the range of 5 to 40 μm (hereinafter, may be referred to as a spherical filler (C)) is blended as an essential component. To do. The shape may be spherical, but this is not limited to a strict true spherical shape, and means that fibrous, needle-like, scaly, plate-like, and indefinite shapes are excluded. Yes, a substantially spherical one may be included. When the spherical term is strictly defined, the cross section (x) obtained by cutting the molded product in the resin flow direction (MD direction) at the time of melt molding and in the direction perpendicular to the MD direction (thickness direction, ND direction). , The cross section (y) cut out in the axial direction (TD direction) and the MD direction, which is perpendicular to the MD direction and perpendicular to the ND direction, and the cross section (z) cut out in the ND direction and the TD direction, respectively, in a scanning electron microscope. (Magnification 1000 times), 50 particles were randomly selected from each SEM image, and the ratio of the major axis of each particle to the minor axis perpendicular to it (minor axis / major axis) was calculated. , It is preferable to define using the sphericity obtained by those arithmetic average values, and the sphericity according to the definition is preferably in the range of 0.6 or more, and in the range of 0.7 or more. Is more preferable, and it is particularly preferable that the content is in the range of 0.8 or more. The maximum sphericity is 1.

The number average particle size of the spherical filler (C) used in the present invention is in the range of 5 to 40 μm, and from the viewpoint of excellent thermal conductivity, it is preferably in the range of 6 μm or more, and more preferably in the range of 7 μm or more. On the other hand, the range of 35 μm or less is preferable, the range of 25 μm or less is more preferable, the range of 20 μm or less is further preferable, and the range of less than 20 μm is particularly preferable, from the viewpoint of excellent fluidity at the time of melting.

The spherical filler (C) used in the present invention is not particularly limited as long as the number average particle diameter is in the above range, and various fillers having a substantially spherical shape can be used. As such a spherical filler (C), magnesium carbonate, calcium carbonate, glass beads, silica and the like can be used, and magnesium carbonate and calcium carbonate are preferable, and magnesium carbonate is most preferable. As the spherical filler (C) used in the present invention, either a commercially available product or a synthetic product may be used, and the present invention is not particularly limited.

In the method for producing a polyarylene sulfide resin composition of the present invention, the compounding ratio of the spherical filler (C) is 100 parts by mass of the polyarylene sulfide resin (A) from the viewpoint of excellent thermal conductivity in the thickness direction of the surface of the molded product. It is preferably 1 to 100 parts by mass, and 5 to 85 parts by mass from the viewpoint of excellent thermal conductivity in the thickness direction of the molded product surface, mechanical strength and smoothness of the molded product surface. It is more preferably in the range of 10 to 75 parts by mass, and further preferably in the range of 10 to 75 parts by mass.

In the present invention, the blending ratio of the whisker (B) and the spherical filler (C) is not particularly limited, but the whisker (B): the spherical filler (C) has a mass ratio of 1:20 to 20. It is preferably in the range of 1, and more preferably in the range of 1:10 to 10: 1.

In the method for producing a polyarylene sulfide resin composition of the present invention, a thermoplastic elastomer can be blended as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluoroelastomers, and silicone-based elastomers, and among them, polyolefin-based elastomers are preferable. When these elastomers are added, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. More preferably, it is in the range of 0.1 to 5 parts by mass. In such a range, the impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.

The polyolefin-based elastomer is, for example, a homopolymerization of α-olefins or a copolymerization of different α-olefins, and when a functional group is further imparted, the α-olefin and a vinyl polymerizable compound having a functional group are used. It can be obtained by copolymerization. Examples of the α-olefin include those in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group includes a carboxy group, an acid anhydride group represented by the formula − (CO) O (CO) −, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group. And so on.

Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and their alkyl esters, maleic acid and fumaric acid. Examples thereof include acids, itaconic acids and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the above-mentioned epoxy group, carboxy group, and acid anhydride group have toughness and It is preferable from the viewpoint of improving impact resistance.

In addition, the method for producing the polyarylene sulfide resin composition of the present invention also includes fillers, silane coupling agents, colorants, antistatic agents, antioxidants, heat-resistant stabilizers, ultraviolet stabilizers, ultraviolet absorbers, and foaming. Known and commonly used additives such as agents, flame retardants, flame retardants, lubricants, and rust preventives can be blended as optional components, if necessary. When these additives are blended, they are appropriately adjusted in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin according to the purpose and application so as not to impair the effects of the present invention. It may be used.

The filler may have any shape such as fibrous, granular, or plate-like as long as it is another filler except for the whisker (B) and the spherical filler (C) used in the present invention. Specifically, glass. Fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium sulfate, calcium silicate and other fibers, natural fibers such as wollastonite, and fibrous fillers such as synthetic fibers. Examples thereof include glass flakes, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. Each of these may be used alone, or two or more types may be used in combination.

The silane coupling agent is, for example, an epoxy group-containing alkoxysilane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ- Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane; γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxy Amino group-containing alkoxysilane compounds such as silane and γ-aminopropyltrimethoxysilane; hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane can be mentioned. Each of these may be used alone, or two or more types may be used in combination.

Further, in the polyarylene sulfide resin composition of the present invention, in addition to the above components, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, poly, as appropriate, depending on the intended use. Sulfon resin, polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluorinated ethylene resin, polydifluorinated ethylene resin, polystyrene resin, ABS resin, phenol A resin, a urethane resin, a synthetic resin such as a liquid crystal polymer, or the like can be blended as an optional component. Further, the blending ratio of these resins differs depending on each purpose and cannot be unconditionally specified, but the present invention is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It may be adjusted and used as appropriate according to the purpose and application so as not to impair the effect of.

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited, and the polyarylene sulfide resin which is an essential component, the whisker (B), the spherical filler, and the above-mentioned optional component to be added as needed. In various forms such as powder, pellets, and strips, put into a ribbon blender, Henshell mixer, V blender, etc. for dry blending, and then a Banbury mixer, mixing roll, single-screw or twin-screw extruder, and kneader. A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range in which the melting point is + 10 ° C. or higher, and more preferably a temperature range in which the melting point is + 10 ° C. to + 100 ° C. More preferably, it can be produced through a step of melt-kneading in a temperature range of melting point +20 to melting point +50 ° C. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.

As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. For example, a resin component discharge amount in the range of 5 to 500 (kg / hr) and a screw rotation speed of 50 to 500 (rpm) are preferable. It is preferable to melt-knead while appropriately adjusting the range of, and it is more preferable to melt-knead under the condition that the ratio (discharge amount / screw rotation speed) is 0.02 to 5 (kg / hr / rpm). .. Further, when the whiskers (B), which is an essential component, and the fibrous filler or additive among the optional components are added, they can be charged into the extruder from the side feeder of the twin-screw kneading extruder. It is preferable from the viewpoint of shape retention and dispersibility. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin input portion to the side feeder with respect to the total screw length of the twin-screw kneading extruder is 0.1 to 0.9. Above all, it is particularly preferable that it is 0.3 to 0.7.

The polyarylene sulfide resin composition of the present invention thus obtained comprises a polyarylene sulfide resin which is an essential component, the whiskers (B), the spherical filler (C), and an optional component added as needed. After the melt-kneading, the melt-kneaded product is processed into pellets, chips, granules, powders, etc. by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary. It is preferable to apply it to various moldings.

The polyarylene sulfide resin composition of the present invention produced by the above-mentioned various production methods uses a polyarylene sulfide resin as a matrix, and the whiskers (B) and the spherical filler (C), which are essential components, are contained in the matrix. By forming a morphology having a structure in which components derived from them and optional components added as necessary are dispersed, mechanical strength is maintained and thermal conductivity is improved.

The polyarylene sulfide resin composition of the present invention can be used for various moldings such as injection molding, compression molding, composite, extrusion molding of sheets, pipes, etc., drawing molding, blow molding, transfer molding, etc. It is also suitable for injection molding because of its excellent properties. When molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably in a temperature range of the melting point + 10 ° C. or higher, more preferably in a temperature range of + 10 ° C. to + 100 ° C. After undergoing the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to a melting point of +50 ° C., the polyarylene sulfide resin composition may be injected into a mold from a resin discharge port for molding. At that time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.

The molded product obtained by molding the polyarylene sulfide resin composition of the present invention not only exhibits excellent thermal conductivity in both the surface direction and the thickness direction with respect to the surface of the molded product, but also the polyarylene sulfide resin. Is excellent in inherent properties and suitable mechanical strength, especially when the molded product has a weld portion, the weld portion has excellent bending strength and tensile strength, and is excellent in lightness, and further, a machine in the TD direction. Excellent in target strength. From this, the polyarylene sulfide resin composition of the present invention can be suitably used as a molded product used as various products and members that require heat dissipation and thermal conductivity.

The use of the molded product is not particularly limited and can be used as various products, but it is particularly preferable to use it as a heat radiating member exhibiting high heat radiating characteristics with respect to a heat source, and the heat generating member or the heat radiating member. It can be used as a bonded composite molded product, a molded product of PAS resin alone, or the like. The heat-generating member to be bonded to the polyarylene sulfide resin composition of the present invention may be an electronic circuit, various other parts capable of generating heat, or a part composed of a heat-dissipating member such as metal such as aluminum die-cast. As a method for joining the composite molded product joined to the heat generating member, for example, insert injection molding, vibration welding, infrared welding, electromagnetic induction heating, and a joining method combining these can be used.

Examples of the molded product and the composite molded product of the polyarylene sulfide resin composition of the present invention include a heat radiating member for an automobile engine control unit or a motor, a heat radiating member for an LED substrate, and various electric / electronic device substrates. A heat sink for the purpose is exemplified. Further, the molded product of the present invention can be not only a heat radiating member but also a normal resin molded product as described below. For example, protection / support members for box-type electric / electronic component integrated modules / multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, etc. Oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, Electric / electronic parts such as parabolic antennas and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / laser discs / compact discs / DVD discs / Blu-ray Home and office electricity represented by audio / video equipment parts such as disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or water supply equipment parts such as water heaters, bath water volume, and temperature sensors. Product parts: Office computer-related parts, telephone equipment-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: microscopes, binoculars, cameras, watches Optical equipment such as, precision machine related parts; Alternator terminal, Alternator connector, Brush holder, Slip ring, IC regulator, Potency meter base for light dial, Relay block, Inhibitor switch, Exhaust gas valve and other various valves, Fuel Related / Exhaust / Intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle Position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dustributor , Starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter Solenoids, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons , Solenoid bobbins, engine oil filters, ignition device cases, and other automobile / vehicle-related parts, and can also be applied to various other applications.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Hereinafter, unless otherwise specified, "%" and "part" are based on mass.

<Examples 1 to 7 and Comparative Examples 1 to 5>
Each material was blended according to the composition components and blending amounts shown in Tables 1 to 3. After that, these compounding materials were put into a twin-screw extruder "TEX-30 (product name)" with a vent manufactured by Japan Steel Works, Ltd., and the resin component discharge amount was 25 kg / hr and the screw rotation speed was 200 rpm. Pellets of the resin composition were obtained by melt-kneading at a set resin temperature of 330 ° C. The glass fiber was charged from the side feeder, and the other materials were uniformly mixed in advance with a tumbler and charged from the top feeder. The pellets of the obtained resin composition were dried in a gear oven at 140 ° C. for 2 hours, and then injection molded to prepare various test pieces, and the following tests were performed. The results of each test are shown in Tables 1 to 3.

<Measurement of MD / TD bending strength>
An ISO TYPE-A dumbbell was prepared as a test piece for evaluation in the flow direction (MD), and an ISO D2 sheet cut out from an ISO D2 sheet for evaluation in the direction perpendicular to the flow (TD) with a width of 25 mm was prepared and used for a measurement test. It was prepared by injecting resin from one end of the dumbbell or the one-point gate of the ISO D2 sheet so that the test piece did not include the welded part.

As a measurement of flexural strength, a test piece composed of the compositions obtained in each Example and Comparative Example was measured in accordance with the measurement method of ISO178 “Plastic-How to determine bending characteristics”.

<Measurement of weld bending strength>
An ISO TYPE-A dumbbell was prepared as a test piece and used for a measurement test. The test piece was prepared by injecting resin from opposite two-point gates at both ends of the dumbbell so as to include a weld portion so that a weld could be formed in a substantially central portion of a narrow parallel portion having a narrow width.

As a measurement of flexural strength, a test piece composed of the compositions obtained in each Example and Comparative Example was measured in accordance with the measurement method of ISO178 “Plastic-How to determine bending characteristics”.

<Measurement of tensile strength>
An ISO TYPE-A dumbbell was prepared as a test piece and used for a measurement test. It was produced by injecting resin from the one-point gate at one end of the dumbbell so that the test piece did not include the welded portion. As the measurement of the tensile strength, a test piece composed of the compositions obtained in each Example and Comparative Example was measured in accordance with the measurement method of JIS K 7161 "Test method of plastic-tensile properties".

<Measurement of weld tensile strength>
An ISO TYPE-A dumbbell was prepared as a test piece and used for a measurement test. The test piece was prepared by injecting resin from the opposing two-point gates at both ends of the dumbbell so as to include the weld portion so that the weld could be formed in the substantially central portion of the narrow parallel portion. As the measurement of the tensile strength, a test piece composed of the compositions obtained in each Example and Comparative Example was measured in accordance with the measurement method of JIS K 7161 "Test method of plastic-tensile properties".

<Charpy impact strength>
An ISO TYPE-A dumbbell was prepared as a test piece and used for a measurement test. It was produced by injecting resin from the one-point gate at one end of the dumbbell so that the test piece did not include the welded portion. The Charpy impact strength is measured for a test piece consisting of the compositions obtained in each Example and Comparative Example in accordance with the measurement method of ISO 179-1 “Plastic-Charpy Impact Characteristics”. It was.

<Measurement of thermal conductivity (xenon flash method)>
As test pieces, flat plates having a length and width of 10 mm and a thickness of 2 mm were prepared for each Example and Comparative Example and used for the test. In the table, MD (Machine Direction) is the resin flow direction during injection molding, ND (Normal Direction) is the direction perpendicular to the MD direction (thickness direction), and TD (Transverse Direction) is the direction perpendicular to the MD direction. And it shall mean the axial direction perpendicular to the ND direction. The measurement of thermal conductivity is composed of the compositions of each Example and Comparative Example in accordance with the measurement method of JIS R 1611 "Measurement method of thermal diffusivity, specific heat capacity and thermal conductivity by flash method of fine ceramics". The test piece was measured.

<Melting viscosity>
V6 melt viscosity of the polyarylene sulfide resin in the examples, the melt viscosity at 300 ° C. (V6), manufactured by Shimadzu Corporation Flow Tester "CFT-500D", 300 ° C., load: 1.96 × ¹⁰ 6 Pa, It is a value measured after holding for 6 minutes under the condition of L / D = 10 (mm) / 1 (mm).

<Measurement of whisker shape>
For the number average fiber diameter and number average fiber length of the whisker component, an SEM image (magnification 1500 times) was obtained by the "ultra-depth multi-angle microscope VHX-D500" manufactured by KEYENCE, and 20 arbitrary fibers in the SEM image were selected. It was measured.

<Measurement of particle size of spherical filler>
The measurement was carried out by a method conforming to the laser diffraction / scattering method (JIS Z8825), and the value calculated as the number average particle diameter of each sample was used.

The compounding ratios of the compounding components in Tables 1 to 3 represent parts by mass, and the following were used.
-PAS resin component A: Polyphenylene sulfide resin (V6 melt viscosity 50 Pa · s)

-Whisker component B-1: wollastonite, number average fiber length 50 μm, number average fiber diameter 4.5 μm, aspect ratio 11
b-2: Basic magnesium sulfate inorganic fiber, number average fiber length 20 μm, number average fiber diameter 1.0 μmm, aspect ratio 20

-Spherical filler component c-1: Magnesium carbonate (number average particle diameter 1 μm)
C-2: Magnesium carbonate (number average particle size 8 μm)
C-3: Magnesium carbonate (number average particle size 18 μm)
C-4: Magnesium carbonate (number average particle size 30 μm)
c-5: Calcium carbonate (number average particle size 50 μm)
-Other filler component c-6: Boron nitride (number average particle diameter 45 μm)

-Other components D: glass fiber, fiber diameter 10 μm, fiber length 3 mm, thermal conductivity 1 (W / m · K)
E: Ethylene / glycidyl methacrylate (88/12% by mass) copolymer

Claims (13)

For heat-dissipating members that melt-knead polyallylen sulfide resin (A), whiskers (B) having a number average fiber diameter of 2 to 50 μm, and spherical fillers (C) having a number average particle diameter of 5 to 40 μm as essential components . A method for producing a polyarylene sulfide resin composition. The whiskers (B) having a number average fiber diameter of 2 to 50 μm are in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), and the number average particle diameter is 5 to 40 μm. The method for producing a polyarylene sulfide resin composition for a heat radiating member according to claim 1, wherein the spherical filler (C) in the range is in the range of 1 to 100 parts by mass. The poly for heat dissipation member according to claim 1 or 2, wherein the whiskers (B) are one or more selected from the group consisting of wollastonite, zinc oxide whiskers, calcium carbonate whiskers, titanium oxide whiskers and magnesium sulfate whiskers. A method for producing an arylene sulfide resin composition. The production of the polyarylene sulfide resin composition for a heat radiating member according to any one of claims 1 to 3, wherein the spherical filler is one or more selected from the group consisting of magnesium carbonate, calcium carbonate, glass beads and silica. Method. It is obtained by melt-kneading a polyarylene sulfide resin (A), a whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm, and a spherical filler (C) having a number average particle diameter in the range of 5 to 40 μm as essential components. A method for manufacturing a heat-dissipating member comprising a molded product, which comprises molding a polyarylene sulfide resin composition. The polyarylene sulfide resin (A), the whiskers (B) having a number average fiber diameter in the range of 2 to 50 μm, and the spherical filler (C) having a number average particle diameter in the range of 5 to 40 μm are blended as essential components. A polyarylene sulfide resin composition for a heat-dissipating member . The whiskers (B) having a number average fiber diameter of 2 to 50 μm are in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), and the number average particle diameter is 5 to 40 μm. The polyarylene sulfide resin composition for a heat radiating member according to claim 6, wherein the spherical filler (C) in the range is in the range of 1 to 100 parts by mass. The poly for heat dissipation member according to claim 6 or 7, wherein the whiskers (B) are one or more selected from the group consisting of wollastonite, zinc oxide whiskers, calcium carbonate whiskers, titanium oxide whiskers and magnesium sulfate whiskers. Allylene sulfide resin composition. The polyarylene sulfide resin composition for a heat radiating member according to any one of claims 6 to 8, wherein the spherical filler is one or more selected from the group consisting of magnesium carbonate, calcium carbonate, glass beads and silica. The polyarylene sulfide resin composition for a heat radiating member according to any one of claims 6 to 9, which is a melt-kneaded product. A heat radiating member made of a molded product obtained by molding the polyarylene sulfide resin composition according to any one of claims 6 to 10. A heat radiating member made of a molded product having a weld portion, which is formed by molding the polyarylene sulfide resin composition according to any one of claims 6 to 10. A method for using a molded product obtained by molding the polyarylene sulfide resin composition according to any one of claims 6 to 10 as a heat radiating member.