Polyarylene sulfide resin composition and insert molded product

Abstract

A polyarylene sulfide resin composition comprising: (A) 100 parts by mass of a polyarylene sulfide resin having a carboxyl terminal and a predetermined melt viscosity; (B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of greater than 10,000 nm and less than 3,000,000 nm and an aspect ratio of greater than 2,000 and less than 500,000; (B2) 0.01 to 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atoms); or (B3) 0.01 to 5 parts by mass of a carbon nanostructure; and (C) 1.0 to 45.0 parts by mass of an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms.

Description

Technical Field

[0001] The present invention relates to a polyarylene sulfide resin composition and an insert molded article. Background Art

[0002] Polyarylene sulfide resins (hereinafter referred to as "PAS resins"), typified by polyphenylene sulfide resins (hereinafter referred to as "PPS resins"), have high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Therefore, they are widely used as materials for components in electrical and electronic equipment, automotive equipment, and chemical equipment. However, PAS resins have a slow crystallization rate, resulting in long molding cycles and the generation of frequent burrs during molding.

[0003] Adding various alkoxysilane compounds is known as a method for reducing burr formation (see Patent Documents 1 and 2). These compounds have been shown to be highly reactive with PAS resins and are believed to improve mechanical properties and suppress burr formation. However, these burr suppression effects are limited and do not fully meet market demand. Furthermore, they do not also accelerate crystallization.

[0004] To address the above-mentioned issues, a resin composition has been proposed that mixes specific carbon nanotubes and, if necessary, an inorganic filler in specific amounts with a specific PAS resin (see Patent Document 3). Furthermore, a resin composition has been proposed that contains two PPS resins having different melt viscosities, kaolin or attapulgite having a predetermined average particle size, or a mixture thereof (see Patent Document 4).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Publication No. 6-21169

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 1-146955

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 2006-143827

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 09-157525 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] The carbon nanotubes used in the resin composition described in Patent Document 3 have an average diameter of 5 to 100 nm and an aspect ratio of 50 to 2000, and are different from the carbon nanotubes that are the subject of the present invention. In addition, in Patent Document 4, kaolin, attapulgite, or a mixture thereof with a specified average particle size is "considered to have the effect of imparting thixotropy to the material (the effect of increasing the shear rate dependence of the melt viscosity), and it is believed that the melt viscosity of the material increases rapidly during the pressure holding process of injection molding (the process in which the shear rate decreases), and the generation of burrs is greatly reduced." In other words, it is mainly recorded that, considering that inorganic fillers such as kaolin are used for the purpose of rapidly increasing the melt viscosity of the material during injection molding, an amount exceeding a fixed amount is required, and in fact, 10 to 150 parts by weight is preferably used relative to 100 parts by weight of the PPS resin composition. Although the generation of burrs can be suppressed by adding inorganic fillers such as kaolin, there is a concern that adding too much will lead to other problems such as reduced moldability and strength.

[0013] On the other hand, PAS resin itself is known to be weak and brittle, lacking in toughness. For example, its durability when insert-molded articles are exposed to alternating high and low temperatures, known as thermal shock resistance, is poor. If a PAS resin composition could achieve both reduced burr formation and excellent thermal shock resistance, its applicability would be further enhanced.

[0014] The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a polyarylene sulfide resin composition capable of achieving both suppression of burr generation and excellent thermal shock resistance.

[0015] Solutions to Problems

[0016] One embodiment of the present invention for achieving the above-mentioned object is as follows.

[0017] (1) A polyarylene sulfide resin composition comprising: (A) 100 parts by mass of a polyarylene sulfide resin, wherein the polyarylene sulfide resin is subjected to a shearing reaction at a temperature of 310° C. and a shearing rate of 1200 sec -1 The melt viscosity measured under 5 to 500 Pa·s and having a carboxyl terminal;

[0018] (B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of greater than 10,000 nm and less than 3,000,000 nm and an aspect ratio of greater than 2,000 and less than 500,000, (B2) 0.01 to 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atoms), or (B3) 0.01 to 5 parts by mass of carbon nanostructures; and

[0019] (C) 1.0 to 45.0 parts by mass of an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms.

[0020] (2) The polyarylene sulfide resin composition according to (1), further comprising 5 to 250 parts by mass of (D) an inorganic filler (excluding the (B1) carbon nanotubes, the (B2) inorganic nanotubes, and the (B3) carbon nanostructures) relative to 100 parts by mass of the (A) polyarylene sulfide resin.

[0021] (3) The polyarylene sulfide resin composition according to (2), wherein the inorganic filler (D) is a fibrous inorganic filler.

[0022] (4) The polyarylene sulfide resin composition according to (2), wherein the inorganic filler (D) is composed of a combination of a fibrous inorganic filler, a plate-like inorganic filler, and / or a particulate inorganic filler.

[0023] (5) The polyarylene sulfide resin composition according to any one of (1) to (4), wherein the (C) olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms is at least one olefin-based copolymer selected from the group consisting of (C1), (C2), and (C3), wherein:

[0024] (C1) is an olefin-based copolymer containing at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, a glycidyl group, an isocyanate group, an isothiocyanate group, an acetoxy group, a silanol group, an alkoxysilyl group, an alkynyl group, an oxazoline group, a mercapto group, a sulfonic acid group, a sulfonate residue, and a carboxylate group;

[0025] (C2) is an olefin-based copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms; and

[0026] (C3) is an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms and a structural unit derived from an α,β-unsaturated carboxylic acid alkyl ester.

[0027] (6) The polyarylene sulfide resin composition according to (5), wherein the (C1) olefin-based copolymer contains a structural unit derived from a glycidyl ester of an α,β-unsaturated acid.

[0028] (7) The polyarylene sulfide resin composition according to (5) or (6), wherein the (C1) olefin-based copolymer is at least one olefin-based copolymer selected from the group consisting of maleic anhydride-modified ethylene-based copolymers, glycidyl methacrylate-modified ethylene-based copolymers, and glycidyl ether-modified ethylene-based copolymers.

[0029] (8) The polyarylene sulfide resin composition according to any one of (5) to (7), wherein the (C1) olefin-based copolymer further contains a structural unit derived from an alkyl (meth)acrylate.

[0030] (9) An insert molded article comprising: a resin component containing the polyarylene sulfide resin composition according to any one of (1) to (8) above; and an insert component containing a metal, an alloy, or an inorganic solid material.

[0031] Effects of the Invention

[0032] According to the present invention, it is possible to provide a polyarylene sulfide resin composition that can achieve both suppression of burr generation and excellent thermal shock resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The drawings show a test piece used in a thermal shock resistance test, (a) is a perspective view, and (b) is a top view.

[0034] Figure 2 To express Figure 1 The drawings of the embedded component of the test piece shown are: (a) a perspective view, and (b) an enlarged top view of the acute-angled portion.

[0035] Figure 3 For about Figure 1 The diagrams illustrating the dimensions of the test piece shown are: (a) a top view and (b) a side view. DETAILED DESCRIPTION

[0036] The polyarylene sulfide resin composition of this embodiment contains: (A) 100 parts by mass of a polyarylene sulfide resin, wherein the polyarylene sulfide resin is subjected to a temperature of 310° C. and a shear rate of 1200 sec -1 The invention further comprises: (B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of greater than 10,000 nm and less than 3,000,000 nm and an aspect ratio of greater than 2,000 and less than 500,000; (B2) 0.01 to 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atoms); or (B3) 0.01 to 5 parts by mass of carbon nanostructures. Furthermore, the invention further comprises (C) 1.0 to 45.0 parts by mass of an olefin-based copolymer containing structural units derived from an α-olefin having 2 or more carbon atoms.

[0037] The PAS resin composition of this embodiment can suppress the generation of burrs during injection molding by containing a predetermined amount of (B1) carbon nanotubes (hereinafter also referred to as "CNTs"), (B2) inorganic nanotubes, or (B3) carbon nanostructures (hereinafter also referred to as "CNS"). The suppression of burrs by the inclusion of components (B1) to (B3) is presumably based on the following mechanism.

[0038] (B1)CNT

[0039] The mechanism by which CNTs with a specific length and aspect ratio suppress burrs is speculated to be due to increased melt viscosity in the low shear rate range and an increase in the crystallization rate (increased solidification rate due to the nucleating agent effect). Furthermore, the increased melt viscosity in the low shear rate range can reduce demolding resistance, while the increased crystallization rate can shorten the molding cycle.

[0040] (B2) Inorganic nanotubes

[0041] The mechanism by which the addition of inorganic nanotubes suppresses burrs is presumably due to an increase in the crystallization rate (increased curing speed due to the nucleating agent effect). Furthermore, the increased crystallization rate can shorten the molding cycle.

[0042] (B3)CNS

[0043] The mechanism by which CNS suppresses burrs is speculated to be due to an increase in melt viscosity in the low shear rate region and an increase in the crystallization rate (increased solidification rate due to the nucleating agent effect). Furthermore, the increase in melt viscosity in the low shear rate region can reduce demolding resistance, while the increase in crystallization rate can shorten the molding cycle.

[0044] In addition, in this embodiment, "nucleating agent" is synonymous with "crystallization nucleating agent", "nucleating agent" and the like.

[0045] On the other hand, the PAS resin composition of this embodiment has excellent thermal shock resistance by including (C) an olefin copolymer containing structural units derived from an α-olefin having 2 or more carbon atoms. The mechanism by which the thermal shock resistance is improved by including the olefin copolymer (C) is that the inclusion of the olefin copolymer (C) facilitates the imparting of flexibility to the resin component, and the softening of the resin component by imparting flexibility contributes to the improvement of thermal shock resistance. Among these, olefin copolymers containing structural units derived from ethylene and structural units derived from an α-olefin having 3 or more carbon atoms, and olefin copolymers containing structural units derived from an α-olefin having 2 or more carbon atoms and structural units derived from an α,β-unsaturated carboxylic acid alkyl ester, facilitate the imparting of flexibility to the resin component.

[0046] It is also speculated that when the olefin-based copolymer (C) contains a specific functional group, this functional group reacts with the terminal group of the PAS resin. This reaction enhances the interaction between the PAS resin and the olefin-based copolymer, further improving thermal shock resistance. Specifically, this functional group is preferably a functional group that reacts with the carboxyl terminal of the PAS resin.

[0047] Thermal shock resistance is also improved by including the components (B1) to (B3). The mechanism is not clear, but is clear based on experimental facts (see Examples below).

[0048] Hereinafter, each component of the PAS resin composition of this embodiment will be described.

[0049] [(A) Polyarylene sulfide resin]

[0050] PAS resin has excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties, as well as good processability.

[0051] The PAS resin is a polymer compound mainly composed of -(Ar-S)- (wherein Ar is an arylene group) as a repeating unit. In this embodiment, a PAS resin having a generally known molecular structure can be used.

[0052] Examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p,p'-diphenylenesulfonyl, p,p'-biphenylene, p,p'-diphenylether, p,p'-diphenylenecarbonyl, and naphthyl. The PAS resin may be a homopolymer consisting solely of the above-mentioned repeating units, or a copolymer containing different types of repeating units as described below, preferably from the viewpoint of processability.

[0053] As a homopolymer, a polyphenylene sulfide resin using p-phenylene as the arylene group and having p-phenylene sulfide groups as repeating units is preferably used. In addition, as a copolymer, among the arylene sulfide groups formed by the aforementioned arylene groups, a combination of two or more different types can be used, but a combination containing p-phenylene sulfide groups and m-phenylene sulfide groups is particularly preferred. Among them, it is more suitable to contain 70 mol% or more, preferably 80 mol% or more, of p-phenylene sulfide groups, from the perspective of physical properties such as heat resistance, moldability, and mechanical properties. In addition, among these PAS resins, a high molecular weight polymer with a substantially linear structure obtained by polycondensation of monomers based on difunctional halogen aromatic compounds can be particularly preferably used. In addition, the PAS resin used in this embodiment can also be used by mixing two or more different types of PAS resins with different molecular weights.

[0054] In addition to linear PAS resins, polymers that have partially formed branched or crosslinked structures by using a small amount of a monomer such as a polyhalogenated aromatic compound having three or more halogen substituents during polycondensation can also be used. Furthermore, polymers that have improved moldability by increasing the melt viscosity through oxidative crosslinking or thermal crosslinking by heating a low-molecular-weight linear polymer at high temperatures in the presence of oxygen or the like can also be used.

[0055] PAS resin can be produced by conventional polymerization methods. PAS resin produced by conventional polymerization methods is typically washed several times with water or acetone to remove by-product impurities, followed by cleaning with acetic acid, ammonium chloride, or the like. This results in the PAS resin containing carboxyl groups at a predetermined ratio at its terminals.

[0056] From the viewpoint of the balance between mechanical properties and fluidity, the melt viscosity (310°C, shear rate 1200 sec) of the PAS resin used as the matrix resin in this embodiment is -1 ), including the case of the above-mentioned mixed system, a PAS resin with a melt viscosity of 5 to 500 Pa·s is used. The melt viscosity of the PAS resin is preferably 7 to 300 Pa·s, more preferably 10 to 250 Pa·s, and particularly preferably 13 to 200 Pa·s.

[0057] In addition, the PAS resin composition of the present embodiment, in the scope of not damaging its effect, as resin component, except PAS resin, also can comprise other resin components.As other resin components, it is not particularly limited, for example, polyethylene resin, polypropylene resin, polyamide resin, polyacetal resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, liquid crystal resin, fluororesin, cyclic olefin resin (cyclic olefin polymer, cyclic olefin copolymer etc.), thermoplastic elastomer, silicon-based polymer, various biodegradable resins etc. can be listed.In addition, two or more resin components can be used in combination.Wherein, from the viewpoint of mechanical properties, electrical properties, physical and chemical characteristics, processability etc., preferably use polyamide resin, modified polyphenylene ether resin, liquid crystal resin etc.

[0058] [(B) Carbon nanotubes, inorganic nanotubes, carbon nanostructures]

[0059] Next, (B1) carbon nanotubes, (B2) inorganic nanotubes, and (B3) carbon nanostructures will be described.

[0060] (B1) Carbon nanotubes (CNTs)

[0061] The CNTs used in this embodiment have a length exceeding 10,000 nm and not more than 3,000,000 nm, and an aspect ratio exceeding 2,000 and not more than 500,000. By using these CNTs, even a relatively small amount of addition can suppress the generation of burrs. Furthermore, the CNTs used in this embodiment can be either single-walled carbon nanotubes or multi-walled carbon nanotubes.

[0062] Here, the aspect ratio of the CNT is a value obtained by dividing the length of the CNT by the diameter of the CNT, and a manufacturer's value (a value announced by the manufacturer in a catalog or the like) may be employed.

[0063] In the CNTs involved in this embodiment, a length exceeding 10,000 nm and not exceeding 3,000,000 nm and an aspect ratio exceeding 2,000 and not exceeding 500,000 can complement each other to suppress the generation of burrs. The length of the CNT is preferably 11,000 to 1,500,000 nm, more preferably 12,000 to 500,000 nm. Furthermore, the aspect ratio of the CNT is preferably 2,010 to 250,000, more preferably 2,030 to 100,000. Furthermore, the diameter of the CNT is preferably 5 to 100 nm, more preferably 7 to 50 nm.

[0064] In this embodiment, 0.05 to 1.5 parts by mass of CNTs are contained relative to 100 parts by mass of PAS resin. When the CNT content is less than 0.05 parts by mass, the generation of burrs cannot be suppressed. In addition, when the CNT content exceeds 1.5 parts by mass, conductivity is easily imparted. The PAS resin composition of this embodiment is suitable for insert moldings because it has excellent heat shock resistance. However, when used for insert moldings, the PAS resin composition of this embodiment preferably maintains insulation. The CNT content is preferably 0.1 to 1.4 parts by mass, and more preferably 0.2 to 1.3 parts by mass.

[0065] As the CNT according to the present embodiment, commercially available products include CP1002M manufactured by LG Chem Co., Ltd. and NTF series manufactured by High Pressure Gas Industries, Ltd.

[0066] [(B2) Inorganic nanotubes]

[0067] In this embodiment, as described above, the suppression of burr generation by inorganic nanotubes is believed to be due to the increase in curing speed due to the effect of the nucleating agent. Therefore, even a relatively small amount of addition can suppress the generation of burrs. In addition, in this embodiment, the inorganic nanotubes are limited to nanotubes that do not contain carbon atoms. Therefore, in this embodiment, the inorganic nanotubes do not contain carbon nanotubes. In addition, inorganic nanotubes are tubular inorganic substances with a diameter of the nanometer scale. Moreover, inorganic nanotubes generally have more insulating properties. If inorganic nanotubes with insulating properties are used, the insulating properties of the PAS resin composition will not be reduced. In this respect, it is different from nanotubes using carbon nanotubes.

[0068] Examples of the inorganic nanotubes used in this embodiment include aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes.

[0069] Aluminosilicate nanotubes are preferably halloysite nanotubes or metahalloysite nanotubes, and among them, halloysite nanotubes are preferred from the viewpoints of low cost and availability.

[0070] Examples of metal sulfide nanotubes include molybdenum sulfide, tungsten sulfide, and copper sulfide nanotubes, and examples of metal halide nanotubes include nickel chloride, cadmium chloride, and cadmium iodide nanotubes.

[0071] In this embodiment, the average length of the inorganic nanotubes is preferably 100 nm to 20 μm, more preferably 500 nm to 15 μm, even more preferably 1 to 10 μm, and particularly preferably 1 to 5 μm. Furthermore, the average outer diameter of the inorganic nanotubes is preferably 5 to 100 nm, more preferably 10 to 80 nm, and even more preferably 30 to 70 nm. Furthermore, the aspect ratio of the inorganic nanotubes is preferably 1 to 4000, and more preferably 5 to 2000.

[0072] Here, the aspect ratio of the inorganic nanotube is a value obtained by dividing the length of the inorganic nanotube by the diameter of the inorganic nanotube, and a manufacturer's value (a value announced by the manufacturer in a catalog or the like) may be employed.

[0073] The PAS resin composition of this embodiment contains 0.01 to 10 parts by mass of inorganic nanotubes per 100 parts by mass of the PAS resin. If the content is less than 0.01 parts by mass, the effect of suppressing burr formation is insufficient, while if the content is greater than 10 parts by mass, mechanical properties such as Charpy impact strength tend to deteriorate. The content of the inorganic nanotubes is preferably 0.5 to 9.9 parts by mass, and more preferably 1.0 to 9.5 parts by mass.

[0074] Among the inorganic nanotubes according to the present embodiment, halloysite nanotubes are commercially available, such as Halloysite G (685445) manufactured by Applied Minerals.

[0075] [(B3) Carbon nanostructure (CNS)]

[0076] The CNS used in this embodiment is a structure containing multiple carbon nanotubes bonded together, with the carbon nanotubes being connected to other carbon nanotubes via branched bonds or crosslinks. Details of such CNS are described in U.S. Patent Application Publication No. 2013-0071565, U.S. Patent No. 9,113,031, U.S. Patent No. 9,447,259, and U.S. Patent No. 9,111,658.

[0077] The CNS used in this embodiment may also be a commercially available product. For example, ATHLOS 200 or ATHLOS 100 manufactured by CABOT may be used. The average fiber diameter of the carbon nanotubes in ATHLOS 200, the smallest unit constituting the CNS, is approximately 10 nm. The average fiber diameter of the carbon nanotubes in ATHLOS 200, the smallest unit constituting the CNS, may be, for example, 0.1 to 50 nm, preferably 0.1 to 30 nm.

[0078] In the present embodiment, 0.01 to 5 parts by mass of CNS are added relative to 100 parts by mass of thermoplastic resin. When the amount of the CNS added is less than 0.01 parts by mass, the suppression of burr generation becomes insufficient. When it exceeds 5 parts by mass, there is a tendency for the viscosity to increase significantly, and the moldability is easily deteriorated. The amount of the CNS added is preferably 0.05 to 3 parts by mass, more preferably 0.15 to 2.5 parts by mass, and particularly preferably 0.5 to 1.7 parts by mass. In addition, as described above, the PAS resin composition of the present embodiment has excellent heat shock resistance and is therefore suitable for insert moldings. In the case of insert moldings, the PAS resin composition of the present embodiment maintains insulation. From this point of view, the amount of the CNS added is preferably 0.01 to 0.5 parts by mass, more preferably 0.03 to 0.45 parts by mass, further preferably 0.05 to 0.4 parts by mass, and particularly preferably 0.1 to 0.35 parts by mass.

[0079] In this embodiment, the method for adding components (B1) to (B3) to the PAS resin is not particularly limited and can be performed by conventionally known methods. Examples of the timing for adding components (B1) to (B3) include during the polymerization of the PAS resin and during melt kneading of the raw materials when preparing a PAS resin composition.

[0080] When preparing a PAS resin composition, components (B1) to (B3) may be added during melt-kneading of the raw materials. For example, the addition may be made after heating and melt-kneading the PAS resin and components (B1) to (B3) to form a pelletized masterbatch. In this case, a resin other than PAS resin may be used to prepare the masterbatch, as long as the burr suppression effect of components (B1) to (B3) is not impaired.

[0081] Alternatively, the PAS resin and components (B1) to (B3) may be added only after a mixture is prepared by stirring. In this case, dry mixing of the PAS resin and components (B1) to (B3) may be employed, or mixing using a tumbler or Henshelmixer mixer may be employed.

[0082] As a method for mixing the PAS resin and components (B1) to (B3) and melt-kneading them, for example, the PAS resin and components (B1) to (B3) may be supplied to an extruder separately, or the PAS resin, components (B1) to (B3), and other compounding agents may be dry-blended and then supplied to the extruder, or part of the raw materials may be supplied by side feeding.

[0083] [(C) Olefin-based copolymer]

[0084] The olefin copolymer (C) used in this embodiment contains structural units derived from an α-olefin having 2 or more carbon atoms. This olefin copolymer is used to improve thermal shock resistance. Specifically, as described above, the inclusion of this olefin copolymer facilitates imparting flexibility to the resin component. This imparted flexibility softens the resin component, contributing to improved thermal shock resistance.

[0085] The (C) olefin-based copolymer is preferably at least one olefin-based copolymer selected from the group consisting of the following (C1) olefin-based copolymers, (C2) olefin-based copolymers, and (C3) olefin-based copolymers, wherein:

[0086] (C1) is an olefin-based copolymer containing at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, a glycidyl group, an isocyanate group, an isothiocyanate group, an acetoxy group, a silanol group, an alkoxysilyl group, an alkynyl group, an oxazoline group, a mercapto group, a sulfonic acid group, a sulfonate residue, and a carboxylate group;

[0087] (C2) is an olefin-based copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms; and

[0088] (C3) is an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms and a structural unit derived from an α,β-unsaturated carboxylic acid alkyl ester.

[0089] In this embodiment, the olefin-based copolymers (C1) to (C3) may be used alone or in combination of two or more. Each of the olefin-based copolymers (C1) to (C3) will be described in detail below.

[0090] ((C1) Olefin-based copolymer)

[0091] The (C1) olefin copolymer is an olefin copolymer containing the above-mentioned specific functional group. That is, the (C1) olefin copolymer is an olefin copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms and the above-mentioned specific functional group. When the olefin copolymer contains the above-mentioned specific functional group, the functional group reacts with the terminal group of the PAS resin, thereby improving the interaction between the PAS resin and the olefin copolymer. It is speculated that the heat shock resistance is further improved by improving this interaction. It is preferred that the functional group is a functional group that reacts with the carboxyl terminal group of the PAS resin. Among the above-mentioned functional groups, an acid anhydride group, an epoxy group, and a glycidyl group are more preferred, and an epoxy group and a glycidyl group are further preferred.

[0092] First, the structural unit derived from an α-olefin having 2 or more carbon atoms will be described below.

[0093] 《Structural unit derived from α-olefin having 2 or more carbon atoms》

[0094] The α-olefin having 2 or more carbon atoms (hereinafter also referred to as "α-olefin") is not particularly limited, and examples thereof include ethylene, propylene, butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 4-methyl-1-hexene. Among them, ethylene is preferred. One type of the α-olefin may be used alone, or two or more types may be used in combination. The content of the structural unit derived from the α-olefin is not particularly limited, but may be, for example, 0.5 to 20% by mass of the total resin composition.

[0095] Examples of the glycidyl group- or epoxy group-containing olefin copolymer (C1) include olefin copolymers having glycidyl esters, glycidyl ethers, or the like in side chains, and olefin copolymers having double bonds in which the double bond moieties are epoxidized.

[0096] As a more specific form of the glycidyl- or epoxy-containing olefin (co)polymer involved, there can be cited olefin copolymers in which monomers having glycidyl or epoxy groups are copolymerized. In particular, it is suitable to use glycidyl-containing olefin copolymers obtained by copolymerizing α-olefins and glycidyl esters of α,β-unsaturated acids.

[0097] The (C1) olefin-based copolymer preferably contains, in addition to structural units derived from α-olefins having 2 or more carbon atoms, structural units derived from glycidyl esters of α,β-unsaturated acids. Structural units derived from glycidyl esters of α,β-unsaturated acids are described below. In this specification, alkyl (meth)acrylates are also referred to as (meth)alkyl acrylates. For example, glycidyl (meth)acrylate is also referred to as glycidyl (meth)acrylate. In this specification, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid, and "(meth)acrylate" refers to both acrylate and methacrylate.

[0098] Structural units derived from glycidyl esters of α,β-unsaturated acids

[0099] The glycidyl ester of an α,β-unsaturated acid (hereinafter sometimes simply referred to as “glycidyl ester”) is not particularly limited, and examples thereof include glycidyl esters having a structure represented by the following general formula (1).

[0100] [Chemical Formula 1]

[0101]

[0102] [In the general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]

[0103] Examples of the compound represented by the general formula (1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferred. One type of glycidyl ester of an α,β-unsaturated acid may be used alone, or two or more types may be used in combination. The content of the structural unit derived from the glycidyl ester of an α,β-unsaturated acid is preferably 0.02 to 2.5% by mass of the total resin composition, more preferably 0.05 to 1.5% by mass, and particularly preferably 0.08 to 1.0% by mass. When the content of the structural unit derived from the glycidyl ester of an α,β-unsaturated acid is within this range, heat shock resistance can be maintained and the precipitation of mold deposits can be further suppressed.

[0104] Furthermore, the olefin-based copolymer (C1) preferably contains structural units derived from an alkyl (meth)acrylate. It is particularly preferred to contain structural units derived from a glycidyl ester of an α,β-unsaturated acid and structural units derived from an alkyl (meth)acrylate. Structural units derived from an alkyl (meth)acrylate are described below.

[0105] 《Structural units derived from alkyl (meth)acrylates》

[0106] There are no particular limitations on the alkyl (meth)acrylates, and examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-pentyl acrylate, and n-octyl acrylate; and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-pentyl methacrylate, and n-octyl methacrylate. Among these, methyl acrylate is particularly preferred. One type of alkyl (meth)acrylate may be used alone, or two or more types may be used in combination. The content of the copolymerization component derived from the alkyl (meth)acrylate is not particularly limited, but may be, for example, 0.2 to 5.5% by mass of the total resin composition.

[0107] More specifically, examples of the olefin copolymer (C1) include maleic anhydride-modified ethylene copolymers, glycidyl methacrylate-modified ethylene copolymers, glycidyl ether-modified ethylene copolymers, and ethylene alkyl acrylate copolymers. Among these, at least one olefin copolymer selected from the group consisting of maleic anhydride-modified ethylene copolymers, glycidyl methacrylate-modified ethylene copolymers, and glycidyl ether-modified ethylene copolymers is preferred, and glycidyl methacrylate-modified ethylene copolymers are most preferred.

[0108] Examples of glycidyl methacrylate-modified ethylene copolymers include glycidyl methacrylate graft-modified ethylene copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-methacrylate copolymers, ethylene-glycidyl methacrylate-ethylacrylate copolymers, ethylene-glycidyl methacrylate-propylacrylate copolymers, and ethylene-glycidyl methacrylate-butylacrylate copolymers. Among these, ethylene-glycidyl methacrylate copolymers and ethylene-glycidyl methacrylate-methacrylate copolymers are preferred because they provide particularly excellent heat shock resistance, and ethylene-glycidyl methacrylate-methacrylate copolymers are particularly preferred. Specific examples of ethylene-glycidyl methacrylate copolymers and ethylene-glycidyl methacrylate-methacrylate copolymers include "BONDFAST" (manufactured by Sumitomo Chemical Co., Ltd.).

[0109] Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymers and glycidyl ether-ethylene copolymers.

[0110] ((C2) an olefin-based copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms)

[0111] (C2) is an olefin-based copolymer containing ethylene and an α-olefin having 3 or more carbon atoms as copolymer components. In the (C2) olefin-based copolymer, the carbon number of the α-olefin is preferably 3 to 20, more preferably 5 to 20, and even more preferably 5 to 15. In addition, as examples of α-olefins having 3 or more carbon atoms, olefins having 3 or more carbon atoms among the structural units derived from the above-mentioned α-olefins having 2 or more carbon atoms can be listed. In addition, the (C2) olefin-based copolymer can be a random copolymer or a block copolymer. The (C2) olefin-based copolymer can be a copolymer formed by 5 to 95% by mass of ethylene and 5 to 95% by mass of α-olefin. Specific examples of the (C2) olefin-based copolymer include ethylene-octene copolymer (EO), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, ethylene-heptene copolymer, etc., and these copolymers can also be mixed and used.

[0112] ((C3) an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms and a structural unit derived from an α,β-unsaturated carboxylic acid alkyl ester)

[0113] (C3) is an olefin-based copolymer containing, as copolymerization components, structural units derived from an α-olefin having 2 or more carbon atoms and structural units derived from an α,β-unsaturated carboxylic acid alkyl ester. Furthermore, it may be a random, block, or graft copolymer, or a copolymer modified with at least one member selected from the group consisting of unsaturated carboxylic acids, their anhydrides, and their derivatives (excluding those meeting the criteria for olefin-based copolymers (C1)).

[0114] Since the structural unit derived from an α-olefin having 2 or more carbon atoms has been described above, the structural unit derived from an α,β-unsaturated carboxylic acid alkyl ester will be described below.

[0115] 《Structural unit derived from α,β-unsaturated carboxylic acid alkyl ester》

[0116] As the α,β-unsaturated carboxylic acid alkyl ester, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, etc. can be used.

[0117] Unsaturated carboxylic acids or their anhydrides used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methylmaleic anhydride, maleic anhydride, methylmaleic anhydride, citraconic anhydride, and the like. One or more of these can be used.

[0118] Specific examples of the olefin-based copolymer C3 include copolymers of ethylene and (meth)acrylic acid esters, such as ethylene ethyl acrylate copolymer (EEA) and ethylene methyl methacrylate copolymer.

[0119] The olefin copolymer (C) contains structural units derived from α-olefins as copolymer components, thereby easily imparting flexibility to the resin component. Imparting flexibility softens the resin component, which contributes to improved thermal shock resistance. From this perspective, among the above olefin copolymers (C), preferably, (C2) is an olefin copolymer containing structural units derived from ethylene and structural units derived from α-olefins having 3 or more carbon atoms, and (C3) is an olefin copolymer containing structural units derived from α-olefins having 2 or more carbon atoms and structural units derived from α,β-unsaturated carboxylic acid alkyl esters.

[0120] Among the above olefin-based copolymers (C1) to (C3), it is preferred to contain the (C1) olefin-based copolymer alone, or to contain the (C1) olefin-based copolymer together with the (C2) olefin-based copolymer and / or the (C3) olefin-based copolymer.

[0121] The olefin copolymers (C1) to (C3) can be prepared by copolymerization using a conventionally known method. For example, the olefin copolymers (C1) to (C3) can be obtained by copolymerization using a generally known free radical polymerization reaction. The type of olefin copolymer is not particularly limited, and it can be, for example, a random copolymer or a block copolymer. In addition, among the olefin copolymers, for example, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, poly-2-ethylhexyl (meth)acrylate, polystyrene, polyacrylonitrile, acrylonitrile-styrene copolymer, butyl (meth)acrylate-styrene copolymer, etc. can also be olefin graft copolymers chemically bonded in a branched or cross-linked structure.

[0122] In the PAS resin composition of the present embodiment, the (C) olefin copolymer contains 1.0 to 45.0 parts by mass relative to 100 parts by mass of the PAS resin. When the olefin copolymer is less than 1.0 parts by mass, it is difficult to fully improve the heat shock resistance. When it exceeds 45.0 parts by mass, the fluidity decreases or the gas generation increases during molding, which easily leads to poor molding. On the other hand, when the olefin copolymer is added, the melt viscosity of the resin composition tends to increase, so there is a tendency for the burrs to become shorter than before the addition of the olefin copolymer. From the viewpoint of the effect of suppressing the generation of burrs with the (a) to (c) components described later, the balance between fluidity and moldability, and the effect of improving heat shock resistance, the olefin copolymer preferably contains 2.0 to 30.0 parts by mass, more preferably 3.5 to 25.0 parts by mass, further preferably 4.0 to 20.0 parts by mass, and particularly preferably 4.0 to 15.0 parts by mass.

[0123] The (C) olefin-based copolymer used in the present embodiment may contain other structural units derived from copolymerization components within a range not hindering the effects thereof.

[0124] [(D) Inorganic filler]

[0125] The PAS resin composition of this embodiment preferably contains (D) an inorganic filler (but excluding (B1) carbon nanotubes, (B2) inorganic nanotubes, and (B3) carbon nanostructures). Inorganic fillers can further improve mechanical strength, thermal shock resistance, heat resistance, etc., and therefore preferably contain fibrous inorganic fillers. In particular, the combined use of a fibrous inorganic filler having a circular cross-section and a fibrous inorganic filler having a flat cross-section further improves thermal shock resistance, making this a preferred method.

[0126] Furthermore, when the (D) inorganic filler is formed of a combination of a fibrous inorganic filler and a plate-like inorganic filler and / or a particulate inorganic filler, the mechanical strength and flatness can be further improved, which is preferred.

[0127] In the present embodiment, "fibrous" refers to a shape with a diameter ratio of 1 to 4 and an average fiber length (cut length) of 0.01 to 3 mm. In addition, "plate-like" refers to a shape with a diameter ratio greater than 4 and an aspect ratio of 1 to 500. Moreover, "powder-granular" refers to a shape with a diameter ratio of 1 to 4 and an aspect ratio of 1 to 2 (including spherical). All shapes are initial shapes (shapes before melt kneading). The diameter ratio refers to "the long diameter of the section at right angles to the length direction (the longest straight line distance of the section) / the short diameter of the section (the longest straight line distance between the long diameter and the right angle direction)". The aspect ratio refers to "the longest straight line distance in the length direction / the short diameter of the section at right angles to the length direction (the longest straight line distance in the section and the longest straight line distance in the right angle direction)". Both the diameter ratio and the aspect ratio can be calculated using a scanning electron microscope and image processing software. In addition, the average fiber length (cut length) can adopt the manufacturer's value (the value published by the manufacturer in the catalog, etc.).

[0128] Examples of fibrous inorganic fillers include mineral fibers such as glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and metal fibrous materials such as stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, and brass fiber. One or more of these can be used. Among them, glass fiber is preferred.

[0129] Examples of marketed glass fiber products include chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 μm) manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (CS03DE 416A, average fiber diameter: 6 μm) manufactured by Owens Corning Co., Ltd., chopped glass fiber (ECS03T-747H, average fiber diameter: 10.5 μm) manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747, average fiber diameter: 13 μm) manufactured by Nippon Electric Glass Co., Ltd., special-shaped cross-section chopped strands (CSG3PA-830, long diameter 28 μm, short diameter 7 μm) manufactured by Nitto Bosho Co., Ltd., and special-shaped cross-section chopped strands (CSG3PL-962, long diameter 20 μm, short diameter 10 μm) manufactured by Nitto Bosho Co., Ltd.

[0130] Fibrous inorganic fillers can be surface-treated with various commonly known surface treatment agents, such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. This surface treatment can improve adhesion to the PAS resin. The surface treatment agent can be applied to the fibrous inorganic filler before material preparation to treat or tighten the surface, or it can be added during material preparation.

[0131] The fiber diameter of the fibrous inorganic filler is not particularly limited, but in the initial shape (shape before melt kneading), it can be, for example, 5 μm to 30 μm. Here, the fiber diameter of the fibrous inorganic filler refers to the major axis of the fiber cross section of the fibrous inorganic filler.

[0132] The cross-sectional shape of the fibrous inorganic filler is not particularly limited, but can list out circular shape, flat shape etc. In addition, the fibrous inorganic filler with different cross-sectional shapes can also be used. When the cross-sectional shape is that the fibrous inorganic filler with circular shape and the cross-sectional shape are the fibrous inorganic filler with flat shape, thermal shock resistance can be further improved, so preferred.

[0133] Examples of plate-like inorganic fillers include glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), and various metal foils. One or more of these can be used, and glass flakes and talc are preferred.

[0134] Examples of commercially available glass sheets include REFG-108 manufactured by Nippon Sheet Glass Co., Ltd. (average particle size (50% d): 623 μm), fine flake manufactured by Nippon Sheet Glass Co., Ltd. (average particle size (50% d): 169 μm), REFG-301 manufactured by Nippon Sheet Glass Co., Ltd. (average particle size (50% d): 155 μm), and REFG-401 manufactured by Nippon Sheet Glass Co., Ltd. (average particle size (50% d): 310 μm).

[0135] Examples of commercially available talc products include crown talc PP manufactured by Matsumura Sangyo Co., Ltd. and talc PKNN manufactured by Hayashi Kasei Co., Ltd.

[0136] The plate-like inorganic filler may be surface-treated in the same manner as the fibrous inorganic filler.

[0137] Examples of the powdery or particulate inorganic filler include carbon black, silicon dioxide, quartz powder, glass beads, glass powder, talc (granular), silicates such as calcium silicate, aluminum silicate, and diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, and aluminum oxide (granular), metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, and various metal powders. One or more of these can be used. Calcium carbonate and glass beads are preferred.

[0138] Examples of marketed products of calcium carbonate include whiten P-30 (average particle size (50% d): 5 μm) manufactured by Toyo Fine Chemistry Co., Ltd. Examples of marketed products of glass beads include EGB731A (average particle size (50% d): 20 μm) manufactured by Potters-Ballotini Co., Ltd. and EMB-10 (average particle size (50% d): 5 μm) manufactured by Potters-Ballotini Co., Ltd.

[0139] The powdery or particulate inorganic filler may be surface-treated in the same manner as the fibrous inorganic filler.

[0140] When the (D) inorganic filler is formed of a combination of a fibrous inorganic filler and a plate-like inorganic filler and / or a particulate inorganic filler, the mechanical strength and flatness can be further improved, which is preferred.

[0141] Examples of combinations of fibrous inorganic fillers and plate-like inorganic fillers and / or particulate inorganic fillers include combinations of glass fiber and glass flakes, glass fiber and calcium carbonate, glass fiber and glass beads, glass fiber and glass flakes and calcium carbonate, glass fiber and glass fiber with a special cross-section (flat shape) and calcium carbonate, etc.

[0142] In the PAS resin composition of this embodiment, the (D) inorganic filler is preferably contained in an amount of 5 to 250 parts by mass per 100 parts by mass of the PAS resin. When the inorganic filler is contained in an amount of 5 to 250 parts by mass, sufficient mechanical properties and fluidity can be achieved. The inorganic filler is more preferably contained in an amount of 15 to 200 parts by mass, further preferably 25 to 150 parts by mass, and particularly preferably 30 to 110 parts by mass.

[0143] [Other ingredients]

[0144] In this embodiment, in addition to the above-mentioned components, known additives generally added to thermoplastic resins and thermosetting resins may be mixed to impart desired properties corresponding to their purpose, such as mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystallization nucleating agents, various antioxidants, heat stabilizers, weathering stabilizers, and preservatives, in order to impart desired properties corresponding to their purpose, within the range not impairing their effects. Furthermore, while the PAS resin composition of this embodiment can suppress the generation of burrs, burr suppressors such as alkoxysilane compounds or branched polyphenylene sulfide-based resins with very high melt viscosities, such as those described in International Publication Nos. 2006 / 068161 and 2006 / 068159, may also be used in combination as needed.

[0145] [Molded products, insert molded products]

[0146] The PAS resin composition of the present embodiment is particularly excellent in thermal shock resistance and is therefore useful when applied to molded articles or insert-molded articles requiring thermal shock resistance.

[0147] The method for forming a molded article using the PAS resin composition of this embodiment is not particularly limited, and various methods known in the art can be employed. For example, the PAS resin composition of this embodiment can be placed in an extruder for melt-kneading and pelletizing, and then the pellets can be placed in an injection molding machine equipped with a specified mold for injection molding. Furthermore, since the resulting molded article uses the PAS resin composition of this embodiment, the generation of burrs is minimized.

[0148] Examples of molded articles formed by molding the PAS resin composition of this embodiment include electrical and electronic equipment parts, automotive equipment parts, chemical equipment parts, and water supply-related parts. Specifically, examples include various automotive cooling system parts, ignition-related parts, switchboard parts, various sensor parts, various actuator parts, throttle valve parts, power module parts, ECU parts, various connector parts, piping connectors (pipe connectors), and joints.

[0149] In addition, other applications include electrical and electronic components such as LEDs, sensors, sockets, terminal boards, printed circuit boards, motor parts, and ECU cases, lighting components, television components, rice cooker components, microwave oven components, iron components, copier-related components, printer-related components, fax machine-related components, heaters, air conditioner components, and other home and office electrical appliance components.

[0150] On the other hand, insert-molded articles are obtained by insert molding a resin component comprising the PAS resin composition of this embodiment and an insert component comprising a metal, alloy, or inorganic solid object. Specifically, the insert-molded article of this embodiment comprises a resin component comprising the PAS resin composition of this embodiment and an insert component comprising a metal, alloy, or inorganic solid object. Because the insert-molded article of this embodiment comprises a PAS resin composition that suppresses burr generation and exhibits excellent thermal shock resistance, the resin component exhibits minimal burr and excellent thermal shock resistance.

[0151] The insert molded product of this embodiment is a composite molded product made by pre-installing metal, etc. on a molding die and filling the outside of the mold with the above-mentioned mixed PAS resin composition. As the molding method for filling the resin into the mold, there are injection molding, extrusion compression molding, etc., but injection molding is generally used. In addition, the shape and size of the insert molded product are not particularly limited. In addition, since the raw materials of the embedded resin are used for the purpose of exerting their characteristics and making up for the shortcomings of the resin, materials that do not change shape or melt when in contact with the resin during molding are used. Therefore, mainly used are inorganic solid materials such as metals such as aluminum, magnesium, copper, iron, brass and their alloys, glass, and pottery that are pre-molded into flat plates, rods, pins, screws, etc. In addition, there are no particular restrictions on the shape of the embedded parts.

[0152] Examples of parts to which the insert molded article of this embodiment is applied include the same examples as those given above for parts to which the molded article obtained by molding the PAS resin composition of this embodiment is applied, and examples include parts having an insert component in part.

[0153] Example

[0154] The present embodiment will be described in more detail below with reference to examples, but the interpretation of the present embodiment is not limited to these examples.

[0155] [Examples 1 to 8, Comparative Examples 1 to 6]

[0156] In each of the Examples and Comparative Examples, the raw material components listed in Tables 1 and 2 were dry-blended, fed into a twin-screw extruder at a cylinder temperature of 320°C (glass fiber was added separately via the side feed of the extruder), melt-kneaded, and pelletized. In Tables 1 and 2, the values for each component are expressed in parts by mass.

[0157] In addition, the details of each raw material component used are shown below.

[0158] (1)PAS resin

[0159] PPS resin 1: Fortron KPS manufactured by KUREHA Co., Ltd. (melt viscosity: 130 Pa·s (shear rate: 1200 sec -1 , 310℃))

[0160] PPS resin 2: Fortron KPS manufactured by KUREHA Co., Ltd. (melt viscosity: 20 Pa·s (shear rate: 1200 sec -1 , 310℃))

[0161] (Measurement of Melt Viscosity of PPS Resin)

[0162] The melt viscosity of the PPS resin is measured in the following manner.

[0163] The capillary rheometer (capillograph) manufactured by Toyo Seiki Co., Ltd. was used. The flat die is used as a capillary and the measurement is performed at a barrel temperature of 310°C and a shear rate of 1200 sec. -1 The melt viscosity is below .

[0164] (2) Carbon nanotubes (CNTs)

[0165] CNT: CP1002M manufactured by LG Chem (average diameter: 9 nm, average length: 19,000 nm, aspect ratio: 2111)

[0166] (3) Olefin copolymers

[0167] Olefin copolymer C1-1 (glycidyl group-containing olefin copolymer): BONDFAST (registered trademark) BF-7L manufactured by Sumitomo Chemical Co., Ltd. (ethylene-glycidyl dimethacrylate-methacrylate copolymer, glycidyl methacrylate content: 3% by mass)

[0168] Olefin copolymer C1-2 (glycidyl group-containing olefin copolymer): BONDFAST (registered trademark) 7M (ethylene-glycidyl dimethacrylate-methacrylate copolymer, glycidyl methacrylate content: 6% by mass) manufactured by Sumitomo Chemical Co., Ltd.

[0169] Olefin copolymer C2: Ethylene-octene copolymer, Engage 8440 manufactured by Dow Chemical Japan Ltd.

[0170] Olefin copolymer C3: Ethylene ethyl acrylate copolymer, NUC-6570 manufactured by NUC Corporation

[0171] (4) Inorganic fillers

[0172] Glass fiber: Chopped strand ECS 03T-747H (fiber diameter: 10.5 μm, length: 3 mm) manufactured by Nippon Electric Glass Co., Ltd.

[0173] Calcium carbonate: MC-35W manufactured by Asahi Mining Co., Ltd. (average particle size (50% d) 25 μm)

[0174] [evaluate]

[0175] The following evaluations were performed using the obtained pellets of each example and comparative example.

[0176] (1) Burr length

[0177] Burr measurement was performed on a portion of the mold with a 20μm mold gap. Injection molding was performed using a mold with a disk-shaped cavity on the outer periphery at a cylinder temperature of 320°C and a mold temperature of 150°C, using the minimum pressure required to completely fill the cavity. The length of the burr generated in this portion was then magnified and measured using an image projector (Mitutoyo Co., Ltd. CNC image measuring system (Model: QVBHU404-PRO1F)). The measurement results are shown in Tables 1 and 2.

[0178] (2) Melt viscosity of the resin composition

[0179] A capillary rheometer (capillograph) manufactured by Toyo Seiki Co., Ltd. was used. The flat die is used as a capillary and the measurement is performed at a barrel temperature of 310°C and a shear rate of 1000 sec. -1 The measurement results are shown in Tables 1 and 2.

[0180] (3) Thermal shock resistance

[0181] (Thermal shock resistance test)

[0182] First, using the pellets obtained in each embodiment and comparative example and a metal insert component, insert molding was performed. Figures 1 to 3 The test piece shown. Figure 1 is a diagram showing the insert-molded test piece 1, Figure 2 1 is a diagram showing an embedded component 11. Figure 3 is a diagram showing the dimensions of the specimen 1. Figure 1 As shown in FIG. 1 , a cylindrical resin component 10 formed of a resin composition is molded by filling a metal insert component 11. The cylindrical resin component 10 is molded using the pellets obtained in the above manner. The insert component 11 is as shown in FIG. Figure 2 As shown, it is a columnar shape, and the shape of its upper surface and bottom surface is a tear-shaped shape with an arc shape on one side and an acute angle shape on the other side. The acute angle shape part is shown as a partial enlarged view. Figure 1 As shown in (b), the front end is arc-shaped and its curvature radius r is 0.2 mm. In addition, the embedded component 11 is higher than the height of the cylindrical resin component 10, and its part protrudes (refer to Figure 1 (a)). Moreover, if Figure 3 As shown in (a), the center O1 of the circle of which the arc of the embedded component 11 is a part does not coincide with the center O2 of the circle of the resin component 10, and the acute angle side of the embedded component 11 is arranged close to the side surface of the resin component 10. Moreover, the distance dw between the front end of the acute angle of the embedded component 11 and the side surface of the resin component 10 is 1 mm, and in the resin component 10, the vicinity of the front end of the acute angle of the embedded component 11 forms a thin-walled welded portion. In addition, Figure 3 The dimensions of the test piece are shown in , and the unit is mm.

[0183] The test pieces were subjected to a thermal shock test chamber (manufactured by Espec Corporation) where a cycle of cooling at -40°C for 1.5 hours and then heating at 180°C for 1.5 hours was repeated. The welds were observed after every 20 cycles. The number of cycles required for cracks to form in the welds was used as an indicator of thermal shock resistance. The evaluation results are shown in Tables 1 and 2.

[0184] [Table 1]

[0185]

[0186] [Table 2]

[0187]

[0188] Table 1 shows that the combined use of an olefin copolymer and CNTs, primarily based on the comparison of Comparative Example 1 and Examples 1-2, which differ in whether or not they contain CNTs, and Comparative Example 3 and Examples 3-4, results in shorter burr length and superior thermal shock resistance. Furthermore, Comparative Example 2, which is substantially identical to Example 2 except that it does not contain an olefin copolymer, exhibits inferior thermal shock resistance. Similarly, Comparative Example 4, which is substantially identical to Example 4 except that it does not contain an olefin copolymer, exhibits inferior thermal shock resistance. As shown above, the inclusion of a specified amount of an olefin copolymer and CNTs allows for suppression of burr formation and superior thermal shock resistance.

[0189] In addition, from another perspective, according to the comparison of Comparative Example 5 containing neither olefin copolymer nor CNT and Comparative Example 1 containing olefin copolymer without CNT and Examples 1-2 (PAS resin is PPS resin 1, and the content of other components is the same), when olefin copolymer is contained, the heat shock resistance is improved, the burr length is shortened, but the burr suppression effect is insufficient. By further adding CNT in addition to the olefin copolymer, not only the burr is suppressed, but also the improvement of heat shock resistance is confirmed. The same situation is also true in the comparison of Comparative Example 6 containing neither olefin copolymer nor CNT and Comparative Example 3 containing olefin copolymer without CNT and Examples 3-4 (PAS resin is PPS resin 2, and the content of other components is the same).

[0190] Furthermore, the comparison of Comparative Example 1 and Examples 1 and 2, and the comparison of Comparative Example 3 and Examples 3 and 4, which have different CNT contents, shows that the thermal shock resistance improves significantly as the CNT content increases. In other words, it is shown that the thermal shock resistance is also improved by the inclusion of CNTs.

[0191] On the other hand, Examples 5 and 6 are examples of systems in which the 6.2 parts by mass of olefin copolymer (C1-1) in Example 1 was replaced with a combination of 3.1 parts by mass of olefin copolymer (C1-1) and 3.1 parts by mass of olefin copolymer (C2) or (C3). Similarly, Examples 7 and 8 are examples of systems in which the 13.9 parts by mass of olefin copolymer (C1-2) in Example 3 was replaced with a combination of 7.0 parts by mass of olefin copolymer (C1-2) and 7.0 parts by mass of olefin copolymer (C2) or (C3). It can be seen that all of Examples 5 to 8 exhibited shortened burr length and excellent thermal shock resistance.

[0192] Comparative Example 5 is almost the same as Example 1 except for the CNTs and olefin copolymer, and Comparative Example 6 is almost the same as Example 3 except for the CNTs and olefin copolymer. It is found that both Comparative Examples 5 and 6 have increased burr length and poor thermal shock resistance.

[0193] Label Description

[0194] 1 Specimen

[0195] 10 resin parts

[0196] 11 Embedded components.

Claims

1. A polyarylene sulfide resin composition, characterized in that Contains: (A) 100 parts by mass of polyarylene sulfide resin, wherein the polyarylene sulfide resin is heated at a temperature of 310° C. and a shear rate of 1200 sec -1 The melt viscosity measured under 5 to 500 Pa·s and having a carboxyl terminal; (B)(B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of greater than 10,000 nm and less than 3,000,000 nm and an aspect ratio of greater than 2,000 and less than 500,000; as well as (C) 1.0 to 45.0 parts by mass of an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms.

2. The polyarylene sulfide resin composition according to claim 1, characterized in that The invention further comprises 5 to 250 parts by mass of (D) an inorganic filler relative to 100 parts by mass of the (A) polyarylene sulfide resin, wherein the inorganic filler does not include the (B1) carbon nanotubes.

3. The polyarylene sulfide resin composition according to claim 2, characterized in that The (D) inorganic filler is a fibrous inorganic filler.

4. The polyarylene sulfide resin composition according to claim 2, characterized in that The (D) inorganic filler is composed of a combination of a plate-like inorganic filler, a powdery or particulate inorganic filler, and a fibrous inorganic filler.

5. The polyarylene sulfide resin composition according to claim 2, characterized in that The (D) inorganic filler is composed of a combination of a plate-like inorganic filler or a powdery or particulate inorganic filler and a fibrous inorganic filler.

6. The polyarylene sulfide resin composition according to any one of claims 1 to 5, characterized in that The olefin copolymer (C) containing a structural unit derived from an α-olefin having 2 or more carbon atoms is at least one olefin copolymer selected from the group consisting of the following (C1), (C2) and (C3), wherein: (C1) is an olefin-based copolymer containing at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, a glycidyl group, an isocyanate group, an isothiocyanate group, an acetoxy group, a silanol group, an alkoxysilyl group, an alkynyl group, an oxazoline group, a mercapto group, a sulfonic acid group, a sulfonate residue, and a carboxylate group; (C2) is an olefin-based copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms; and (C3) is an olefin-based copolymer containing a structural unit derived from an α-olefin having 2 or more carbon atoms and a structural unit derived from an α,β-unsaturated carboxylic acid alkyl ester.

7. The polyarylene sulfide resin composition according to claim 6, characterized in that The (C1) olefin-based copolymer contains a structural unit derived from a glycidyl ester of an α,β-unsaturated acid.

8. The polyarylene sulfide resin composition according to claim 6, characterized in that The (C1) olefin-based copolymer is at least one olefin-based copolymer selected from the group consisting of maleic anhydride-modified ethylene-based copolymers, glycidyl methacrylate-modified ethylene-based copolymers, and glycidyl ether-modified ethylene-based copolymers.

9. The polyarylene sulfide resin composition according to claim 6, characterized in that The (C1) olefin-based copolymer further contains a structural unit derived from an alkyl (meth)acrylate.

10. An insert molded product, characterized in that The invention comprises a resin component comprising the polyarylene sulfide resin composition according to any one of claims 1 to 5 and an embedding component comprising a metal, an alloy or an inorganic solid material.

Images