CN117715984A

CN117715984A - Polyarylene sulfide resin composition and insert molded article

Info

Publication number: CN117715984A
Application number: CN202280052982.1A
Authority: CN
Inventors: 金塚龙也; 出井秀和
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 2021-07-30
Filing date: 2022-07-26
Publication date: 2024-03-15
Also published as: WO2023008417A1; JPWO2023008417A1; JP7382541B2

Abstract

A polyarylene sulfide resin composition comprising: (A) 100 parts by mass of a polyarylene sulfide resin having a carboxyl terminal and having a prescribed melt viscosity; (B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of more than 10000nm and 3000000nm or less and an aspect ratio of more than 2000 and 500000 or less, (B2) 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atom), or (B3) 0.01 to 5 parts by mass of carbon nanostructures; and (C) 1.0 to 45.0 parts by mass of an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms.

Description

Polyarylene sulfide resin composition and insert molded article

Technical Field

The present invention relates to a polyarylene sulfide resin composition and an insert molded article.

Background

Polyarylene sulfide resins (hereinafter also referred to as "PAS resins") typified by polyphenylene sulfide resins (hereinafter also referred to as "PPS resins") have high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Therefore, it is widely used for electric and electronic equipment component materials, automobile equipment component materials, chemical equipment component materials, and the like. However, the PAS resin has a slow crystallization rate, and therefore has a long cycle time at the time of molding and a large amount of burrs at the time of molding.

Various alkoxysilane compounds are known as methods for reducing the occurrence of burrs (see patent documents 1 and 2). It has been confirmed that various alkoxysilane compounds have high reactivity with PAS resins, and are considered to have improved mechanical properties, an effect of suppressing burr generation, and the like. However, the effect of suppressing the generation of burrs is limited, and the market demand is not satisfied sufficiently, and the effect of accelerating the crystallization rate is not achieved.

In order to solve the above problems, a resin composition has been proposed in which a specific amount of a specific carbon nanotube and an inorganic filler are mixed with a specific PAS resin as needed (see patent document 3). Further, a resin composition containing two PPS resins having different melt viscosities, kaolin having a predetermined average particle diameter, attapulgite (atapulgite), or a mixture thereof has been proposed (see patent document 4).

Prior art literature

Patent literature

Patent document 1: japanese patent publication No. 6-21169

Patent document 2: japanese patent laid-open No. 1-146955

Patent document 3: japanese patent laid-open No. 2006-143827

Patent document 4: japanese patent laid-open No. 09-157525

Disclosure of Invention

Problems to be solved by the invention

The carbon nanotubes used in the resin composition described in patent document 3 are carbon nanotubes having an average diameter of 5 to 100nm and an aspect ratio of 50 to 2000, and are different from the carbon nanotubes that are the object of the present invention. In patent document 4, it is considered that "kaolin, attapulgite, or a mixture thereof having a predetermined average particle diameter" has an effect of imparting thixotropic properties to a material (an effect of improving the shear rate dependency of melt viscosity), and that the melt viscosity of a material rapidly increases and the generation of burrs is greatly reduced by a pressure maintaining process (a process in which the shear rate becomes small) of injection molding. That is, it is mainly described that since the inorganic filler such as kaolin is used for the purpose of rapidly increasing the melt viscosity of the material in injection molding, it is necessary to fix the amount of the inorganic filler or more, and it is actually preferably 10 to 150 parts by weight based on 100 parts by weight of the PPS resin composition. Although the occurrence of burrs can be suppressed by adding an inorganic filler such as kaolin, there is a concern that the addition amount is large, which may cause other problems such as deterioration in moldability and strength.

On the other hand, it is known that PAS resins themselves are poor in toughness and are weak, and for example, insert molded articles are poor in durability when exposed alternately to high temperatures and low temperatures, so-called thermal shock resistance (high and low temperature shock resistance). In the PAS resin composition, if the inhibition of burr generation and excellent thermal shock resistance can be simultaneously achieved, the applicability is further improved.

The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a polyarylene sulfide resin composition which can achieve both suppression of burr generation and excellent thermal shock resistance.

Means for solving the problems

One mode of the present invention for achieving the above object is as follows.

(1) A polyarylene sulfide resin composition comprising: (A) 100 parts by mass of a polyarylene sulfide resin having a shear rate of 1200sec at a temperature of 310 DEG C ^-1 The melt viscosity measured below is 5 to 500 Pa.s and has a carboxyl terminus;

(B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of more than 10000nm and 3000000nm or less and an aspect ratio of more than 2000 and 500000 or less, (B2) 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atom), or (B3) 0.01 to 5 parts by mass of carbon nanostructures; and

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

(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) per 100 parts by mass of the (a) polyarylene sulfide resin.

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

(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 powdery inorganic filler.

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

(C1) An olefin 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 alkoxysilane group, an alkynyl group, an oxazoline group, a mercapto group, a sulfonic acid group, a sulfonate residue, and a carboxylate group;

(C2) An olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from an alpha-olefin having 3 or more carbon atoms; and

(C3) Is an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms and a structural unit derived from an alkyl ester of an alpha, beta-unsaturated carboxylic acid.

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

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

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

(9) An insert molded article comprising: a resin part comprising the polyarylene sulfide resin composition according to any one of (1) to (8), and an embedded part comprising a metal, an alloy or an inorganic solid.

Effects of the invention

According to the present invention, a polyarylene sulfide resin composition that can achieve both suppression of burr generation and excellent thermal shock resistance can be provided.

Drawings

Fig. 1 is a view showing a test piece used in a thermal shock resistance test, (a) is a perspective view, and (b) is a plan view.

Fig. 2 is a view showing an insert part of the test piece shown in fig. 1, (a) is a perspective view, and (b) is an enlarged plan view of an acute-angled portion.

Fig. 3 is an explanatory diagram of the dimensions of the test piece shown in fig. 1, (a) is a top view, and (b) is a side view.

Detailed Description

The polyarylene sulfide resin composition of the present embodiment contains: (A) 100 parts by mass of a polyarylene sulfide resin having a shear rate of 1200sec at a temperature of 310 DEG C ^-1 The melt viscosity measured below is 5 to 500 Pa.s and has a carboxyl terminus; (B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of more than 10000nm and 3000000nm or less and an aspect ratio of more than 2000 and 500000 or less, (B2) 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes (but limited to nanotubes containing no carbon atom), or (B3) 0.01 to 5 parts by mass of carbon nanostructures. In addition, it also contains (C) 1.0 to the whole range45.0 parts by mass of an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms.

The PAS resin composition of the present embodiment can suppress the occurrence 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 occurrence of burrs is suppressed by containing the components (B1) to (B3), presumably by the following mechanism.

(B1)CNT

The mechanism of suppressing burrs by CNTs having a predetermined length and a predetermined aspect ratio is presumed to be helpful in increasing the melt viscosity and the crystallization rate (the solidification rate due to the effect of the nucleating agent) in the low shear rate region. Further, by increasing the melt viscosity in the low shear rate region, a decrease in mold release resistance can be achieved, and by increasing the crystallization rate, the molding cycle can be shortened.

(B2) Inorganic nanotubes

The mechanism by which burrs can be suppressed by the addition of the inorganic nanotubes is presumed to be helpful in improving the crystallization rate (improving the solidification rate by the effect of the nucleating agent). In addition, the molding cycle can be shortened by increasing the crystallization rate.

(B3)CNS

The mechanism by which burrs can be suppressed by CNS addition is presumed to be helpful in increasing melt viscosity and increasing crystallization rate (increasing solidification rate due to the nucleating agent effect) in the low shear rate region. Further, by increasing the melt viscosity in the low shear rate region, the mold release resistance can be reduced, and by increasing the crystallization rate, the molding cycle can be shortened.

In the present embodiment, the term "nucleating agent" is synonymous with "crystallization nucleating agent", "nucleating agent" and the like.

On the other hand, the PAS resin composition of the present embodiment is excellent in thermal shock resistance by comprising (C) an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms. As a mechanism for improving thermal shock resistance by containing the (C) olefin copolymer, it is considered that the (C) olefin copolymer is contained to easily impart flexibility to the resin member, and softening the resin member by imparting flexibility contributes to improvement of thermal shock resistance. Wherein the flexibility of the resin member is easily imparted to the resin member by an olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from an alpha-olefin having 3 or more carbon atoms, or an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms and a structural unit derived from an alkyl ester of an alpha, beta-unsaturated carboxylic acid.

Further, it is also presumed that when the (C) olefin-based copolymer contains a specific functional group, the functional group reacts with a terminal group of the PAS resin, and by this reaction, the interaction of the PAS resin with the olefin-based copolymer is improved, whereby the thermal shock resistance is further improved. Wherein the functional group is preferably a functional group which reacts with the carboxyl terminal of PAS resin.

The thermal shock resistance is also improved by the inclusion of the components (B1) to (B3). The mechanism is not clear, but is clear based on experimental facts (see examples described later).

The components of the PAS resin composition according to the present embodiment will be described below.

[ (A) polyarylene sulfide resin ]

PAS resins are excellent in mechanical properties, electrical properties, heat resistance and other physical and chemical properties and have good processability.

The PAS resin is mainly a polymer compound composed of- (Ar-S) -wherein Ar is an arylene group as a repeating unit, and a PAS resin having a generally known molecular structure can be used in the present embodiment.

Examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p '-diphenylene sulfo, p' -biphenylene, p '-diphenylene ether, p' -diphenylene carbonyl, and naphthyl. The PAS resin may be a homopolymer comprising only the above-mentioned repeating units, or a copolymer comprising the following repeating units of different types is preferable from the viewpoint of processability and the like.

As the homopolymer, a polyphenylene sulfide resin having a p-phenylene sulfide group as a repeating unit, wherein p-phenylene group is used as an arylene group, is preferably used. Further, as the copolymer, among the arylene sulfide groups formed from the foregoing arylene groups, a combination of two or more kinds different from each other may be used, but among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Among these, the p-phenylene sulfide group is contained in an amount of 70 mol% or more, preferably 80 mol% or more, but is preferable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by polycondensation of a monomer mainly composed of a difunctional halogen aromatic compound can be particularly preferably used. The PAS resin used in the present embodiment may be a mixture of two or more different PAS resins having different molecular weights.

In addition to the PAS resin having a linear structure, a polymer in which a branched structure or a crosslinked structure is partially formed by using a small amount of a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents at the time of polycondensation is also exemplified. Further, a polymer having a low molecular weight and a linear structure is heated at a high temperature in the presence of oxygen or the like, and the melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve molding processability.

The PAS resin may be prepared by a conventionally known polymerization method. The PAS resin produced by a general polymerization method is usually washed several times with water or acetone to remove by-product impurities and the like, and then washed with acetic acid, ammonium chloride and the like. As a result, the carboxyl terminal is contained in a predetermined ratio at the terminal of the PAS resin.

From the viewpoint of balance between mechanical properties and fluidity, the PAS resin as the base resin used in the present embodiment has a melt viscosity (310 ℃ C., shear rate 1200 sec) ^-1 ) PAS resins of 5 to 500 Pa.s are used, including the case of the above-mentioned mixed systems. The melt viscosity of the PAS resin is preferably 7 to 300 Pa.s, more preferably 10 to 250 Pa.s, Particularly preferably 13 to 200 Pa.s.

The PAS resin composition according to the present embodiment may contain other resin components in addition to the PAS resin, as long as the effects are not impaired. The other resin component is not particularly limited, and examples thereof include polyethylene resins, polypropylene resins, polyamide resins, polyacetal resins, modified polyphenylene ether resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins, polyimide resins, polyamideimide resins, polyether imide resins, polysulfone resins, polyether sulfone resins, polyether ketone resins, polyether ether ketone resins, liquid crystal resins, fluorine resins, cycloolefin resins (cycloolefin polymers, cycloolefin copolymers, and the like), thermoplastic elastomers, silicone polymers, and various biodegradable resins. In addition, two or more types of resin components may be used in combination. Among them, polyamide resins, modified polyphenylene ether resins, liquid crystal resins, and the like are preferably used from the viewpoints of mechanical properties, electrical properties, physical and chemical properties, processability, and the like.

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

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

[ (B1) Carbon Nanotubes (CNTs) ]

The CNT used in the present embodiment has a length of more than 10000nm and 3000000nm or less, and an aspect ratio of more than 2000 and 500000 or less. By using this CNT, the occurrence of burrs can be suppressed even when a relatively small amount of CNT is added. The CNT used in the present embodiment may be a single-layer carbon nanotube or a multi-layer carbon nanotube.

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 published by the manufacturer in a catalog or the like) may be employed.

In the CNT according to the present embodiment, the length of more than 10000nm and 3000000nm and the aspect ratio of more than 2000 and 500000 can complement each other to suppress the generation of burrs. The length of the CNTs is preferably 11000 ～ 1500000nm, more preferably 12000 to 500000nm. The aspect ratio of the CNT is preferably 2010 to 250000, more preferably 2030 to 100000. The diameter of the CNTs is preferably 5 to 100nm, more preferably 7 to 50nm.

In the present embodiment, 0.05 to 1.5 parts by mass of CNT is contained per 100 parts by mass of PAS resin. When the CNT is less than 0.05 parts by mass, generation of burrs cannot be suppressed. In addition, when the CNT exceeds 1.5 parts by mass, conductivity is easily imparted. The PAS resin composition of the present embodiment is suitable for insert molded articles because of its excellent thermal shock resistance. However, in the case of being used for an insert molded article, the PAS resin composition of the present embodiment preferably maintains insulation properties. The CNT content is preferably 0.1 to 1.4 parts by mass, more preferably 0.2 to 1.3 parts by mass.

The CNT according to the present embodiment includes CP1002M manufactured by LG chemical company, NTF series manufactured by high-pressure gas industry (ltd), and the like as commercial products.

[ (B2) inorganic nanotubes ]

In the present embodiment, as described above, suppression of burr generation by the inorganic nanotube is considered to be due to an improvement in curing speed based on the effect of the nucleating agent. Therefore, even if the amount of the additive is relatively small, the occurrence of burrs can be suppressed. In addition, in the present embodiment, the inorganic nanotubes are limited to nanotubes containing no carbon atoms. Therefore, in this embodiment, the inorganic nanotubes do not contain carbon nanotubes. In addition, the inorganic nanotubes are tubular inorganic substances whose diameters are nano-scale dimensions. Further, the inorganic nanotubes generally have a large amount of insulating properties, and if the inorganic nanotubes having insulating properties are used, the insulating properties of the PAS resin composition are not lowered. In this respect, it is different from the nanotubes using carbon nanotubes.

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

The aluminosilicate nanotubes are preferably halloysite (halloysite) nanotubes or metahalloysite (metahalloysite) nanotubes. Among them, halloysite nanotubes are preferred from the viewpoints of low cost and availability.

The metal sulfide nanotubes include molybdenum sulfide, tungsten sulfide, copper sulfide nanotubes, and the like. Examples of the metal halide nanotubes include nickel chloride, cadmium chloride, and cadmium iodide nanotubes.

In this embodiment, the average length of the inorganic nanotubes is preferably 100nm to 20. Mu.m, more preferably 500nm to 15. Mu.m, still more preferably 1 to 10. Mu.m, particularly preferably 1 to 5. Mu.m. The average outer diameter of the inorganic nanotubes is preferably 5 to 100nm, more preferably 10 to 80nm, and even more preferably 30 to 70nm. The aspect ratio of the inorganic nanotubes is preferably 1 to 4000, more preferably 5 to 2000.

Here, the aspect ratio of the inorganic nanotubes is a value obtained by dividing the length of the inorganic nanotubes by the diameter of the inorganic nanotubes, and the values of the manufacturer (the values published by the manufacturer in catalogues and the like) may be adopted.

The PAS resin composition of the present embodiment contains 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes relative to 100 parts by mass of PAS resin, and when the amount of inorganic nanotubes is less than 0.01 parts by mass, the effect of suppressing the occurrence of burrs is insufficient, and when the amount of inorganic nanotubes is 10 parts by mass or more, mechanical properties such as Charpy impact strength are easily deteriorated. The content of the inorganic nanotubes is preferably 0.5 to 9.9 parts by mass, more preferably 1.0 to 9.5 parts by mass.

Among the inorganic nanotubes according to the present embodiment, halloysite nanotubes include halloysite G (685445) manufactured by Applied Minerals, inc.

[ (B3) Carbon Nanostructures (CNS) ]

The CNS used in the present embodiment is a structure including a plurality of carbon nanotubes bonded together, and the carbon nanotubes are bonded to other carbon nanotubes through a branched bond or a crosslinked structure. Details of such CNS are described in us patent application publication No. 2013-00715575, us patent No. 9,113,031, us patent No. 9,447,259, us patent No. 9,111,658.

The CNS used in the present embodiment may be a commercially available product. For example, ATHLOS200, ATHLOS100, etc. manufactured by CABOT corporation may be used. Wherein, the average fiber diameter of the carbon nanotubes of ATHLOS200 as the minimum unit constituting the CNS is about 10 nm. The average fiber diameter of the carbon nanotubes, which are the smallest units constituting the CNS, may be, for example, 0.1 to 50nm, and preferably 0.1 to 30nm.

In this embodiment, 0.01 to 5 parts by mass of CNS is added to 100 parts by mass of the thermoplastic resin. When the amount of CNS added is less than 0.01 parts by mass, the suppression of burr generation becomes insufficient, and when it exceeds 5 parts by mass, the viscosity tends to be significantly increased, and the moldability tends to be deteriorated. The amount of 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. Further, as described above, the PAS resin composition according to the present embodiment has excellent thermal shock resistance and is therefore suitable for insert molded articles. When the PAS resin composition of the present embodiment is used in an insert molded article, the amount of the CNS added is preferably 0.01 to 0.5 part by mass, more preferably 0.03 to 0.45 part by mass, still more preferably 0.05 to 0.4 part by mass, and particularly preferably 0.1 to 0.35 part by mass, from the viewpoint that the PAS resin composition maintains insulation.

In the present embodiment, the method of adding the components (B1) to (B3) to the PAS resin is not particularly limited, and may be performed by a conventionally known method. Examples of the timing of adding the components (B1) to (B3) include when polymerizing the PAS resin, when melt-kneading the raw materials in the preparation of the PAS resin composition, and the like.

The timing of adding the components (B1) to (B3) during melt-kneading of the raw materials in the preparation of the PAS resin composition may be, for example, after heating and melt-kneading the PAS resin and the components (B1) to (B3) to form a master batch in pellet form. In this case, the masterbatch may be produced using a resin other than the PAS resin as long as the burr suppressing effect by the components (B1) to (B3) is not impaired.

Further, the PAS resin may be added only after the PAS resin and the components (B1) to (B3) are mixed. In this case, examples of the method of dry-mixing the PAS resin and the components (B1) to (B3) include a mixing method using a drum or a Henschel mixer (Henschel).

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

[ (C) olefin copolymer ]

The (C) olefin copolymer used in the present embodiment contains a structural unit derived from an alpha-olefin having 2 or more carbon atoms. The olefin copolymer is used for improving thermal shock resistance. That is, as described above, the inclusion of the olefin copolymer makes it easy to impart flexibility to the resin member, and the resin member becomes soft due to the imparting of the flexibility, contributing to improvement of thermal shock resistance.

The (C) olefin copolymer is preferably at least one olefin copolymer selected from the group consisting of (C1) olefin copolymers, (C2) olefin copolymers and (C3) olefin copolymers described below,

In the present embodiment, the (C1) to (C3) olefin copolymer may be used singly or in combination of two or more. The olefin copolymers (C1) to (C3) will be described in detail below.

((C1) olefin copolymer)

(C1) The olefin copolymer is an olefin copolymer having the above specific functional group. That is, the (C1) olefin copolymer is an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms and the 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, and the interaction between the PAS resin and the olefin copolymer is promoted. It is presumed that the thermal shock resistance is further improved by the improvement of such interaction. Among them, the functional group is preferably a functional group which reacts with a carboxyl terminal group of the PAS resin. Among the above functional groups, an acid anhydride group, an epoxy group, and a glycidyl group are more preferable, and an epoxy group and a glycidyl group are further preferable.

The structural unit derived from an alpha-olefin having 2 or more carbon atoms will be described first.

Structural units derived from alpha-olefins having 2 or more carbon atoms

Examples of the α -olefin having 2 or more carbon atoms (hereinafter also referred to simply as "α -olefin") include, but are not particularly limited to, ethylene, propylene, butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene, and the like. Among them, ethylene is preferable. The α -olefin may be used singly or in combination of two or more. 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.

Examples of the glycidyl or epoxy group-containing olefin copolymer which is one of the olefin copolymers (C1) include olefin copolymers having a glycidyl ester, a glycidyl ether or the like in a side chain, olefin copolymers having a double bond, and olefin copolymers having a double bond, the double bond portion of which has been subjected to epoxy oxidation.

More specific examples of the glycidyl group-or epoxy group-containing olefin (co) polymer include olefin copolymers obtained by copolymerizing monomers having a glycidyl group or an epoxy group, and particularly, glycidyl group-containing olefin copolymers obtained by copolymerizing an α -olefin and a glycidyl ester of an α, β -unsaturated acid are suitably used.

(C1) The olefin copolymer preferably contains structural units derived from glycidyl esters of α, β -unsaturated acids, in addition to structural units derived from α -olefins having 2 or more carbon atoms. The structural units derived from glycidyl esters of α, β -unsaturated acids are described below. Further, in the present specification, the alkyl (meth) acrylate is also referred to as a (meth) alkyl acrylate. For example, glycidyl (meth) acrylate is also known as glycidyl (meth) acrylate. In this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid, and "(meth) acrylic acid ester" means both acrylic acid ester and methacrylic acid ester.

Structural units derived from glycidyl esters of alpha, beta-unsaturated acids

The glycidyl ester of an α, β -unsaturated acid (hereinafter, also 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).

[ chemical formula 1]

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

Examples of the compound represented by the general formula (1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferable. The glycidyl esters of α, β -unsaturated acids may be used singly or in combination of two or more. 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, more preferably 0.05 to 1.5% by mass, and particularly preferably 0.08 to 1.0% by mass of the total resin composition. When the content of the structural unit derived from the glycidyl ester of an α, β -unsaturated acid is within this range, it is possible to maintain thermal shock resistance and further suppress precipitation of mold deposit.

The (C1) olefin copolymer preferably contains a structural unit derived from an alkyl (meth) acrylate. It is particularly preferred to contain structural units derived from glycidyl esters of α, β -unsaturated acids and structural units derived from alkyl (meth) acrylates. The structural unit derived from the alkyl (meth) acrylate is described below.

Structural units derived from alkyl (meth) acrylates

The alkyl (meth) acrylate is not particularly limited, 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; 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 them, methyl acrylate is particularly preferred. The alkyl (meth) acrylate may be used alone or in combination of two or more. 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 mass% of the total resin composition.

More specifically, examples of the (C1) olefin copolymer include a maleic anhydride-modified ethylene copolymer, a glycidyl methacrylate-modified ethylene copolymer, a glycidyl ether-modified ethylene copolymer, and an ethylene alkyl acrylate copolymer. Among them, at least one olefin copolymer selected from the group consisting of maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer and glycidyl ether-modified ethylene copolymer is preferable, and glycidyl methacrylate-modified ethylene copolymer is most preferable.

Examples of the glycidyl methacrylate-modified ethylene copolymer include a glycidyl methacrylate graft-modified ethylene copolymer, an ethylene-glycidyl methacrylate-methacrylate copolymer, an ethylene-glycidyl methacrylate-ethyl acrylate copolymer, an ethylene-glycidyl methacrylate-propyl acrylate copolymer, and an ethylene-glycidyl methacrylate-butyl acrylate copolymer. Among them, ethylene-glycidyl methacrylate copolymer and ethylene-glycidyl methacrylate-methacrylate copolymer are preferable, and ethylene-glycidyl methacrylate-methacrylate copolymer is particularly preferable, because particularly excellent thermal shock resistance can be obtained. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methacrylate copolymer include "BONDFAST" (manufactured by Sumitomo chemical Co., ltd.).

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

((C2) an olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from an alpha-olefin having 3 or more carbon atoms)

(C2) The olefin copolymer contains ethylene and an alpha-olefin having 3 or more carbon atoms as copolymerization components. (C2) In the olefin copolymer, the carbon number of the α -olefin is preferably 3 to 20, more preferably 5 to 20, and still more preferably 5 to 15. Examples of the alpha-olefin having 3 or more carbon atoms include those having 3 or more carbon atoms among the above-mentioned structural units derived from an alpha-olefin having 2 or more carbon atoms. The (C2) olefin copolymer may be a random copolymer or a block copolymer. (C2) The olefin copolymer may be a copolymer comprising 5 to 95% by mass of ethylene and 5 to 95% by mass of an α -olefin. Specific examples of the (C2) olefin copolymer include ethylene-octene copolymer (EO), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, and ethylene-heptene copolymer, and these copolymers may be used in combination.

((C3) an olefin copolymer containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms and a structural unit derived from an alkyl ester of an alpha, beta-unsaturated carboxylic acid)

(C3) The olefin copolymer contains, as a copolymerization component, a structural unit derived from an alpha-olefin having 2 or more carbon atoms and a structural unit derived from an alkyl ester of an alpha, beta-unsaturated carboxylic acid. Further, it may be a random, block or graft copolymer, or a copolymer modified with at least one selected from the group consisting of unsaturated carboxylic acids and anhydrides thereof and derivatives thereof (in addition, a substance conforming to the (C1) olefin-based copolymer).

Since the structural units derived from an alpha-olefin having 2 or more carbon atoms have been described above, the structural units derived from an alkyl ester of an alpha, beta-unsaturated carboxylic acid will be described below.

Structural units derived from alkyl esters of alpha, beta-unsaturated carboxylic acids

As the alkyl ester of an alpha, beta-unsaturated carboxylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate and the like can be used.

Examples of the unsaturated carboxylic acid or anhydride thereof used as the modifier include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methyl maleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, monomethyl maleate, monoethyl fumarate, methyl itaconate, methyl maleic anhydride, methyl maleic anhydride, and citraconic anhydride, and one or more of them may be used.

Specific examples of the olefin copolymer C3 include ethylene- (meth) acrylate copolymers (EEA), ethylene-methyl methacrylate copolymers, and the like, and copolymers of ethylene and (meth) acrylic acid esters.

(C) The olefin copolymer contains a structural unit derived from an α -olefin as a copolymerization component, thereby easily imparting flexibility to the resin member. The resin member is softened by the imparting of flexibility, which contributes to improvement of thermal shock resistance. From this viewpoint, (C2) is preferably an olefin 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 preferably an olefin 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.

Among the above (C1) to (C3) olefin copolymers, it is preferable to contain the (C1) olefin copolymer alone or both of the (C1) olefin copolymer and the (C2) olefin copolymer and/or the (C3) olefin copolymer.

(C1) The olefin-based copolymer (C3) can be produced by copolymerizing the copolymer by a conventionally known method. For example, the (C1) to (C3) olefin copolymers described above can be obtained by copolymerizing by a generally known radical polymerization reaction. The type of the olefin copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. In addition, among the above-mentioned olefin-based 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, and the like may be olefin-based graft copolymers chemically bonded in a branched or crosslinked structure.

In the PAS resin composition of the present embodiment, the (C) olefin copolymer is contained in an amount of 1.0 to 45.0 parts by mass based on 100 parts by mass of the PAS resin. When the amount of the olefin copolymer is less than 1.0 part by mass, it tends to be difficult to sufficiently improve the thermal shock resistance, and when it exceeds 45.0 parts by mass, the fluidity is lowered or the gas generation during molding is increased, and molding defects are likely to occur. On the other hand, when the olefin copolymer is added, the melt viscosity of the resin composition tends to be high, and therefore burrs tend to be shorter than before the addition of the olefin copolymer. From the viewpoints of the effect of suppressing burrs to be formed by blending with the components (a) to (c) described later, the balance of fluidity and moldability, and the effect of improving thermal 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, still more preferably 4.0 to 20.0 parts by mass, and particularly preferably 4.0 to 15.0 parts by mass.

The olefin copolymer (C) used in the present embodiment may contain other structural units derived from the copolymerization component within a range that does not inhibit the effect.

[ (D) inorganic filler ]

The PAS resin composition of the present embodiment preferably contains (D) an inorganic filler (excluding (B1) carbon nanotubes, (B2) inorganic nanotubes and (B3) carbon nanostructures). Among them, the inorganic filler can further improve mechanical strength, thermal shock resistance, heat resistance, and the like, and therefore, it is preferable to contain a fibrous inorganic filler. In particular, when a fibrous inorganic filler having a circular cross-sectional shape and a fibrous inorganic filler having a flat cross-sectional shape are used in combination, thermal shock resistance can be further improved, which is preferable.

Further, when the inorganic filler (D) is formed of a combination of a fibrous inorganic filler and a plate-like inorganic filler and/or a powdery inorganic filler, mechanical strength and flatness can be further improved, and thus it is preferable.

In the present embodiment, the term "fibrous" means a shape having a diameter-to-diameter ratio of 1 to 4 and an average fiber length (cut length) of 0.01 to 3 mm. The term "plate-like" refers to a shape having a diameter-to-diameter ratio of greater than 4 and an aspect ratio of 1 to 500. The "powder and granular material" refers to a shape (including a spherical shape) having a different diameter ratio of 1 to 4 and an aspect ratio of 1 to 2. Whichever shape is the initial shape (shape before melt-kneading). The different diameter ratio is "the long diameter of a cross section perpendicular to the longitudinal direction (the longest linear distance of the cross section)/the short diameter of the cross section (the longest linear distance of the long diameter and the perpendicular direction)". The aspect ratio is "the longest straight distance in the longitudinal direction/the minor diameter of a cross section at right angles to the longitudinal direction (the longest straight distance in the right angle direction and the longest straight distance in the cross section)". Both the aspect ratio and the reduction ratio can be calculated using a scanning electron microscope and image processing software. In addition, the average fiber length (cut length) may take the manufacturer's value (the value published by the manufacturer in catalogues and the like).

Examples of the fibrous inorganic filler include glass fibers, carbon fibers, zinc oxide fibers, titanium oxide fibers, wollastonite (wollastonite), silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, mineral fibers such as potassium titanate fibers, metal fibrous materials such as stainless steel fibers, aluminum fibers, titanium fibers, copper fibers, brass fibers, and the like, and one or two or more of them may be used. Among them, glass fibers are preferable.

Examples of the glass fiber-made products on the market include chopped glass fibers (ECS 03T-790DE, average fiber diameter: 6 μm) produced by Nitroseline, chopped glass fibers (CS 03DE 416A, average fiber diameter: 6 μm) produced by Eurasian, chopped glass fibers (ECS 03T-747H, average fiber diameter: 10.5 μm) produced by Nitroseline, chopped glass fibers (ECS 03T-747, average fiber diameter: 13 μm) produced by Nitroseline, profiled-section chopped strands (CSG 3PA-830, 28 μm long, 7 μm short) produced by Nitroseline, profiled-section chopped strands (CSG 3PL-962, 20 μm long, 10 μm short) produced by Nitroseline, etc.

The fibrous inorganic filler may be surface-treated with various surface-treating agents such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, fatty acids, and the like, which are generally known. The adhesion to the PAS resin can be improved by the surface treatment. The surface treatment agent may be applied to the fibrous inorganic filler in advance before the material is prepared for the surface treatment or the harvest treatment, or may be added simultaneously at the time of the material preparation.

The fiber diameter of the fibrous inorganic filler is not particularly limited, but may be, for example, 5 μm to 30 μm in the initial shape (shape before melt kneading). The fiber diameter of the fibrous inorganic filler herein refers to the long diameter of the fiber cross section of the fibrous inorganic filler.

The cross-sectional shape of the fibrous inorganic filler is not particularly limited, but circular shape, flat shape, and the like are exemplified. In addition, fibrous inorganic fillers having different cross-sectional shapes may be used in combination. When a fibrous inorganic filler having a circular cross-sectional shape and a fibrous inorganic filler having a flat cross-sectional shape are used in combination, thermal shock resistance can be further improved, and thus it is preferable.

Examples of the plate-like inorganic filler include glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), and various metal foils, and one or two or more of them may be used. Among them, glass flakes and talc are preferable.

As examples of the product on the market of the glass sheet, REFG-108 (average particle size (50% d): 623 μm) made by Nitro (Japan), flake (fine flash) made by Nitro (Japan) (average particle size (50% d): 169 μm), REFG-301 (average particle size (50% d): 155 μm) made by Nitro (Japan), REFG-401 (average particle size (50% d): 310 μm) made by Nitro (Japan) and the like can be given.

Examples of the commercial products of talc include grown talc PP manufactured by soncun industries, inc. And talc PKNN manufactured by Lin Huacheng, inc.

The plate-like inorganic filler may be subjected to a surface treatment in the same manner as the fibrous inorganic filler.

Examples of the particulate inorganic filler include carbon black, silica, quartz powder, glass beads, glass powder, talc (granular), silicate such as calcium silicate, aluminum silicate, diatomaceous earth, metal oxide such as iron oxide, titanium oxide, zinc oxide, alumina (granular), metal carbonate such as calcium carbonate, magnesium carbonate, metal sulfate such as calcium sulfate, barium sulfate, other silicon carbide, silicon nitride, boron nitride, various metal powders, and one or more of them may be used. Among them, calcium carbonate and glass beads are preferable.

As an example of a product on the market of calcium carbonate, there may be mentioned whisten P-30 (average particle size (50% d): 5 μm) manufactured by the east Fine Chemistry Co., ltd. Examples of the products on the market of glass beads include EGB731A (average particle size (50% d): 20 μm) manufactured by potters-ballotini, and EMB-10 (average particle size (50% d): 5 μm) manufactured by potters-ballotini.

The particulate inorganic filler may be subjected to a surface treatment similar to the fibrous inorganic filler.

When the inorganic filler (D) is formed of a combination of a fibrous inorganic filler and a plate-like inorganic filler and/or a powdery inorganic filler, the mechanical strength and the flatness can be further improved, and thus it is preferable.

Examples of the combination of the fibrous inorganic filler and the plate-like inorganic filler and/or the particulate inorganic filler include a combination of glass fibers and glass flakes, glass fibers and calcium carbonate, glass fibers and glass beads, glass fibers and glass flakes and calcium carbonate, glass fibers and glass fibers having a special-shaped cross section (flat shape) and calcium carbonate, and the like.

In the PAS resin composition of the present embodiment, the inorganic filler (D) is preferably contained in an amount of 5 to 250 parts by mass based on 100 parts by mass of the PAS resin. When the inorganic filler is 5 to 250 parts by mass, sufficient mechanical properties and fluidity can be obtained. The inorganic filler is more preferably contained in an amount of 15 to 200 parts by mass, still more preferably contained in an amount of 25 to 150 parts by mass, and particularly preferably contained in an amount of 30 to 110 parts by mass.

[ other Components ]

In the present embodiment, in addition to the above-described components, known additives added to thermoplastic resins and thermosetting resins, that is, mold release agents, colorants such as slip agents, plasticizers, flame retardants, dyes and pigments, crystallization accelerators, crystallization nucleating agents, various antioxidants, heat stabilizers, weather resistance stabilizers, preservatives, and the like may be generally blended in order to impart desired properties corresponding to the purpose thereof, within a range that does not impair the effects. Further, although the PAS resin composition of the present embodiment can suppress the occurrence of burrs, an alkoxysilane compound, for example, a burr suppressing agent such as a branched polyphenylene sulfide resin having a very high melt viscosity as described in International publication No. 2006/068161, international publication No. 2006/068159, or the like may be used in combination as required.

[ molded article, insert molded article ]

The PAS resin composition according to the present embodiment is particularly excellent in thermal shock resistance, and therefore is useful for application to molded articles or insert molded articles requiring thermal shock resistance.

The method for molding the molded article using the PAS resin composition of the present embodiment is not particularly limited, and various methods known in the art can be employed. For example, the PAS resin composition of the present embodiment can be produced by charging the PAS resin composition into an extruder, melt-kneading the PAS resin composition, granulating the PAS resin composition, and injection-molding the granulated PAS resin composition in an injection molding machine equipped with a predetermined mold. Further, the PAS resin composition of the present embodiment is used for the molded article to be obtained, and thus the occurrence of burrs is small.

Examples of the molded article obtained by molding the PAS resin composition of the present embodiment include electric and electronic equipment parts, automobile equipment parts, chemical equipment parts, and water diversion related parts. Specifically, various cooling system components, ignition-related components, distribution board components, various sensor components, various actuator components, throttle valve components, power module components, ECU components, various connector components, piping connectors (pipe connectors), joints, and the like of the automobile are exemplified.

Further, as other applications, for example, electric and electronic parts such as LEDs, sensors, sockets, terminal boards, printed boards, motor parts, ECU cases, etc., lighting parts, television parts, electric cooker parts, microwave oven parts, iron parts, copier-related parts, printer-related parts, facsimile-related parts, heaters, air-conditioning parts, etc., home and office electrical parts are available.

On the other hand, the insert molded article is obtained by insert molding using a resin member comprising the PAS resin composition of the present embodiment and an insert member comprising a metal, an alloy or an inorganic solid. That is, the insert molded article of the present embodiment includes a resin member including the PAS resin composition of the present embodiment and an insert member including a metal, an alloy, or an inorganic solid. Since the insert molded article of the present embodiment contains the PAS resin composition which is suppressed in the occurrence of burrs and is excellent in thermal shock resistance, the resin member is less in burrs and is excellent in thermal shock resistance.

The insert molded article of the present embodiment is a composite molded article obtained by preliminarily mounting a metal or the like on a molding die and filling the outside thereof with the above-described mixed PAS resin composition. Examples of molding methods for filling the resin into the mold include injection molding and extrusion compression molding, but injection molding is general. In addition, the shape and size of the insert molded article are not particularly limited. Further, since the material for embedding the resin is used for the purpose of taking advantage of the characteristics thereof and compensating for the shortage of the resin, a material which does not change or melt when in contact with the resin at the time of molding is used. Therefore, materials in which inorganic solid materials such as metals, glass, and ceramics, such as aluminum, magnesium, copper, iron, and brass, and alloys thereof, are preformed into a flat plate shape, a rod, a pin, and a screw are mainly used. The shape of the insert member is not particularly limited.

As the member to which the insert molded product of the present embodiment is applied, there may be mentioned a member having an insert part in a part of such a member, as in the case of the member to which the molded product obtained by molding the PAS resin composition of the present embodiment described above is applied.

Examples

The present embodiment will be described more specifically by way of examples, but the explanation of the present embodiment is not limited to these examples.

Examples 1 to 8 and comparative examples 1 to 6

In each of examples and comparative examples, each of the raw material components shown in tables 1 to 2 was dry-blended, and then fed into a twin-screw extruder having a cylinder temperature of 320 ℃ (glass fibers were separately fed through a side feed portion of the extruder) to be melt-kneaded, and pelletized. In tables 1 to 2, the numerical values of the respective components represent parts by mass.

The details of the raw material components used are shown below.

(1) PAS resin

PPS resin 1: fortron KPS (melt viscosity: 130 Pa.s (shear rate: 1200 sec) ^-1 、310℃))

PPS resin 2: fortron KPS (melt viscosity: 20 Pa.s (shear rate: 1200 sec) ^-1 、310℃))

(measurement of melt viscosity of PPS resin)

The melt viscosity of the PPS resin was measured in the following manner.

Capillary rheometer (capillograph) manufactured by Toyo Seisakusho, inc., usingThe flat die of (2) was used as a capillary tube, and the shear rate was measured at a cylinder temperature of 310℃and a shear rate of 1200sec ^-1 Melt viscosity below.

(2) Carbon Nanotube (CNT)

CNT: CP1002M manufactured by LG chemical Co., ltd (average diameter: 9nm, average length: 19000nm, aspect ratio: 2111)

(3) Olefin copolymer

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

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

Olefin copolymer C2: ethylene-octene copolymer, engage 8440 manufactured by Dow Chemical Japan

Olefin copolymer C3: ethylene ethyl acrylate copolymer, NUC-6570 manufactured by NUC

(4) Inorganic filler

Glass fiber: chopped strand ECS 03T-747H (fiber diameter: 10.5 μm, length 3 mm) manufactured by Nitro Corp. Of Japan

Calcium carbonate: MC-35W (average particle size (50% d) 25 μm) manufactured by Asahi mineral powder Co., ltd

[ evaluation ]

The following evaluation was performed using the obtained pellets of each of the examples and comparative examples.

(1) Length of burr

A burr measuring section having a die gap of 20 μm was injection molded using a die having a disk-shaped cavity provided on the outer periphery, at a cylinder temperature of 320℃and a die temperature of 150℃with a minimum pressure required for complete cavity filling. Then, the burr length generated in this portion was measured by enlarging it with a CNC image measuring instrument (model: QVBHU404-PRO 1F) manufactured by Mitutoyo. The measurement results are shown in tables 1 to 2.

(2) Melt viscosity of resin composition

Capillary rheometer (capillograph) manufactured by Toyo Seisakusho, inc. was usedThe flat die of (2) was used as a capillary tube, and the shear rate was measured at a cylinder temperature of 310℃and a shear rate of 1000sec ^-1 Melt Viscosity (MV) below. The measurement results are shown in tables 1 to 2.

(3) Thermal shock resistance

(thermal shock resistance test)

First, test pieces shown in fig. 1 to 3 were insert molded using the pellets obtained in each of examples and comparative examples and the metal insert member. Fig. 1 is a diagram showing an insert molded test piece 1, fig. 2 is a diagram showing an insert member 11, and fig. 3 is a diagram showing the dimensions of the test piece 1. As shown in fig. 1, the test piece 1 is molded in a state in which a cylindrical resin member 10 made of a resin composition is filled with a metal insert member 11. The cylindrical resin member 10 is molded using the pellets obtained as described above. As shown in fig. 2, the insert 11 has a columnar shape, and the upper surface and the bottom surface thereof have a tear shape having an arc shape on one side and an acute angle shape on the other side. As shown in fig. 1 (b), which is a partially enlarged view, the acute-angle-shaped portion has a rounded tip with a radius of curvature r of 0.2mm. The embedded member 11 is higher than the cylindrical resin member 10 in height, and a part thereof protrudes (see fig. 1 (a)). As shown in fig. 3 (a), the center O1 of the circle in which the circular arc of the insert member 11 is a part is not aligned with the center O2 of the circle of the resin member 10, and the acute-angle-shaped side of the insert member 11 is disposed so as to be close to the side surface of the resin member 10. The distance dw between the sharp-angled tip of the insert member 11 and the side surface of the resin member 10 is 1mm, and the vicinity of the sharp-angled tip of the insert member 11 is a welded portion having a relatively small thickness in the resin member 10. In addition, the dimensions of the test piece are shown in fig. 3 in mm.

The above test pieces were repeatedly cooled at-40℃for 1.5 hours using a cold and hot impact tester (Espec Co., ltd.) and then heated at 180℃for 1.5 hours, and the welded portions were observed every 20 cycles. The number of cycles when cracking occurred in the welded portion was evaluated as an index of thermal shock resistance. The evaluation results are shown in tables 1 to 2.

TABLE 1

TABLE 2

According to table 1, the comparison of comparative example 1 and examples 1 to 2 and the comparison of comparative example 3 and examples 3 to 4, which differ in whether CNT is contained or not, mainly show that the use of the olefin copolymer and CNT in combination shortens the burr length and is excellent in thermal shock resistance. Further, comparative example 2, which is almost the same as example 2 except that the olefin-based copolymer was not contained, was inferior in thermal shock resistance. Similarly, comparative example 4, which does not contain an olefin copolymer and is almost the same as example 4, has poor thermal shock resistance. From the above, by containing a predetermined amount of the olefin copolymer and CNT, suppression of burr generation and excellent thermal shock resistance can be achieved.

From another point of view, according to comparative example 5 containing no olefin copolymer nor CNT and comparative example 1 containing no CNT and comparative examples 1 and 2 (the PAS resins are PPS resins 1 and the other components are the same), the thermal shock resistance is improved when the olefin copolymer is contained, the burr length is shortened, but the effect of suppressing burrs is insufficient. Further addition of CNT in addition to the olefin copolymer suppresses burrs and improves thermal shock resistance. In the same manner, the same applies to comparative example 6 in which the olefin-based copolymer is not contained and CNT is not contained and comparative example 3 in which the olefin-based copolymer is not contained and comparative examples 3 to 4 (the PAS resins are PPS resin 2 and the other components are contained in the same amounts).

From the comparison of comparative examples 1 and 1 to 2 and the comparison of comparative examples 3 and 3 to 4, which have different CNT contents, it is apparent that the thermal shock resistance is significantly improved as the CNT content is increased. That is, it is shown that thermal shock resistance is also improved by containing CNTs.

On the other hand, examples 5 and 6 are examples of a system in which 6.2 parts by mass of the olefin copolymer (C1-1) in example 1 was changed to 3.1 parts by mass of the olefin copolymer (C1-1) and 3.1 parts by mass of the olefin copolymer (C2) or (C3) were used in combination. Similarly, examples 7 and 8 are examples in which 13.9 parts by mass of the olefin copolymer (C1-2) in example 3 was changed to 7.0 parts by mass of the olefin copolymer (C1-2) and 7.0 parts by mass of the olefin copolymer (C2) or (C3) were used in combination. It is also apparent from any of examples 5 to 8 that the burr length was short and the thermal shock resistance was excellent.

Further, comparative example 5 was almost the same as the example in which CNT and olefin copolymer were removed in example 1, and further, comparative example 6 was almost the same as the example in which CNT and olefin copolymer were removed in example 3. It is found that comparative examples 5 and 6 have long burrs and poor thermal shock resistance.

Description of the reference numerals

1. Test piece

10. Resin component

11. An embedded component.

Claims

1. A polyarylene sulfide resin composition characterized by comprising: (A) 100 parts by mass of a polyarylene sulfide resin having a shear rate of 1200sec at a temperature of 310 DEG C ^-1 The melt viscosity measured below is 5 to 500 Pa.s and has a carboxyl terminus;

(B) (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of more than 10000nm and 3000000nm or less and an aspect ratio of more than 2000 and 500000 or less, (B2) 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes, or (B3) 0.01 to 5 parts by mass of carbon nanostructures, wherein the inorganic nanotubes are limited to nanotubes containing no carbon atoms; and

2. The polyarylene sulfide resin composition according to claim 1, wherein,

the polyarylene sulfide resin (A) further contains 5 to 250 parts by mass of (D) an inorganic filler, wherein the inorganic filler does not include the (B1) carbon nanotubes, the (B2) inorganic nanotubes, and the (B3) carbon nanostructures, with respect to 100 parts by mass of the polyarylene sulfide resin.

3. The polyarylene sulfide resin composition according to claim 2, wherein,

The inorganic filler (D) is fibrous inorganic filler.

4. The polyarylene sulfide resin composition according to claim 2, wherein,

the inorganic filler (D) is composed of a combination of fibrous inorganic filler, plate-like inorganic filler and/or powdery inorganic filler.

5. The polyarylene sulfide resin composition according to any one of claim 1 to 4,

the olefin copolymer (C) containing a structural unit derived from an alpha-olefin having 2 or more carbon atoms is at least one olefin copolymer selected from the group consisting of (C1), (C2) and (C3) described below,

6. The polyarylene sulfide resin composition according to claim 5,

the (C1) olefin copolymer contains structural units derived from glycidyl esters of alpha, beta-unsaturated acids.

7. The polyarylene sulfide resin composition according to claim 5 or 6,

the (C1) olefin copolymer is at least one olefin copolymer selected from the group consisting of maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, and glycidyl ether-modified ethylene copolymer.

8. The polyarylene sulfide resin composition according to any one of claim 5 to 7,

the (C1) olefin copolymer further contains a structural unit derived from an alkyl (meth) acrylate.

9. An insert molded article comprising: a resin part comprising the polyarylene sulfide resin composition according to any one of claims 1 to 8, and an embedded part comprising a metal, an alloy or an inorganic solid.