JP2022096861A - Polyarylene sulfide resin composition - Google Patents

Abstract

To provide a polyarylene sulfide resin composition with less occurrence of burrs.SOLUTION: The polyarylene sulfide resin composition contains 0.01 pt.mass or more and less than 10 pts.mass of inorganic nanotubes (limited to ones containing no carbon atoms) based on 100 pts.mass of a polyarylene sulfide resin having a melt viscosity of 5-500 Pa s as measured at a temperature of 310°C and a shear rate of 1,200 sec-1. The inorganic nanotubes are preferably one kind selected from the group consisting of aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes.SELECTED DRAWING: None

Description

The present invention relates to a polyarylene sulfide resin composition.

Polyphenylene sulfide resin (hereinafter sometimes referred to as "PAS resin") represented by polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS resin") has high heat resistance, mechanical properties, and chemical resistance. Since it has dimensional stability and flame retardancy, it is widely used in electrical and electronic equipment parts materials, automobile equipment parts materials, chemical equipment parts materials, and the like. However, the PAS resin has a problem that the crystallization rate is slow, so that the cycle time at the time of molding is long, and that burrs are frequently generated at the time of molding.

As a method for reducing the generation of burrs, it is known to add various alkoxysilane compounds (see Patent Documents 1 and 2). Various alkoxysilane compounds and PAS resins have high reactivity, and are recognized to have the effects of improving mechanical properties and suppressing the generation of burrs. However, there is a limit to the effect of suppressing the occurrence of burrs, the demands of the market are not fully satisfied, and the effect of increasing the crystallization rate is not achieved at the same time.

In order to solve the above problems, a resin composition in which a specific PAS resin is mixed with a specific amount of a specific carbon nanotube and, if necessary, an inorganic filler has been proposed (see Patent Document 3). In addition, a resin composition containing two types of PPS resins having different melt viscosities and kaolin, attapulsite, or a mixture thereof having a predetermined average particle size has been proposed (see Patent Document 4).

Special Fair 6-21169 Gazette Japanese Unexamined Patent Publication No. 1-146955 Japanese Unexamined Patent Publication No. 2006-143827 Japanese Unexamined Patent Publication No. 09-157525

In the resin composition described in Patent Document 3, it is necessary to add a relatively large amount of carbon nanotubes in order to sufficiently suppress the generation of burrs. Then, the resin composition has conductivity due to the conductivity of the carbon nanotubes. Further, such a resin composition cannot be used for a molded product that requires insulating properties. Further, Patent Document 4 seems to have "an effect of imparting sway modification to a material (an effect of increasing the shear rate dependence of the melt viscosity) for kaolin, attapulsite, or a mixture thereof having a predetermined average particle size. , It is thought that the generation of burrs is greatly reduced by the sudden increase in the melt viscosity of the material in the pressure holding process (the process in which the shear rate decreases) in injection molding. " That is, since an inorganic filler such as kaolin is used for the purpose of increasing the melt viscosity of the material in injection molding at once, it is considered that a certain amount or more is required, and the amount is actually 100 parts by weight of the PPS resin composition. On the other hand, it is stated that 10 to 150 parts by weight is preferable. Although the generation of burrs can be suppressed by adding an inorganic filler such as kaolin, there is a concern that a large amount of the addition may cause other problems such as formability and deterioration of strength.

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 with less generation of burrs.

One aspect of the present invention that solves the above problems is as follows.
(1) Inorganic nanotubes (limited to those containing no carbon atom) with respect to 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 5 to 500 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1200 sec ^-1 . A polyarylene sulfide resin composition containing 0.01 parts by mass or more and less than 10 parts by mass.

(2) The polyarylene according to (1) above, wherein the inorganic nanotube is one selected from the group consisting of aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes. Sulfide resin composition.

(3) The polyarylene sulfide resin composition according to (2) above, wherein the aluminosilicate nanotube is a halloysite nanotube or a meta halloysite nanotube.

(4) Any of the above (1) to (3), further containing 5 to 250 parts by mass of a non-conductive inorganic filler (excluding the inorganic nanotubes) with respect to 100 parts by mass of the polyarylene sulfide resin. The polyarylene sulfide resin composition described in Crab.

(5) The polyarylene sulfide according to (4) above, wherein the non-conductive inorganic filler is one or more selected from the group consisting of glass fibers, glass beads, glass flakes, calcium carbonate and talc. Resin composition.

According to the present invention, it is possible to provide a polyarylene sulfide resin composition with less generation of burrs.

The polyarylene sulfide resin composition of the present embodiment has an inorganic nanotube (provided as carbon) with respect to 100 parts by mass of the polyarylene sulfide resin having a melt viscosity of 5 to 500 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1200 sec ^-1 . (Limited to those containing no atoms)) is contained in an amount of 0.01 parts by mass or more and less than 10 parts by mass.

The PAS resin composition of the present embodiment suppresses the generation of burrs by containing inorganic nanotubes. It is presumed that the mechanism by which burrs are suppressed by the addition of inorganic nanotubes is due to the improvement in the crystallization rate (improvement in the solidification rate due to the effect of the nucleating agent). Further, by improving the crystallization rate, the molding cycle can be shortened. Further, most of the inorganic nanotubes generally have insulating properties, and if the inorganic nanotubes having insulating properties are used, the insulating properties of the PAS resin composition will not be deteriorated. In that respect, it differs from the one using carbon nanotubes.
Hereinafter, each component of the PAS resin composition of the present embodiment will be described.

[Polyarylene sulfide resin]
The PAS resin is characterized by being excellent in mechanical properties, electrical properties, heat resistance and other physical and chemical properties, and having good processability.
The PAS resin is a polymer compound mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit, and is a PAS resin having a molecular structure generally known in the present embodiment. Can be used.

Examples of the arylene group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p'-diphenylene sulphon group, a p, p'-biphenylene group, p, p'-. Examples thereof include a diphenylene ether group, a p, p'-diphenylene carbonyl group and a naphthalene group. The PAS resin may be a homopolymer composed of only the above-mentioned repeating units, or a copolymer containing the following different kinds of repeating units may be preferable from the viewpoint of processability and the like.

As the homopolymer, a polyphenylene sulfide resin using a p-phenylene group as an arylene group and having a p-phenylene sulfide group as a repeating unit is preferably used. Further, as the copolymer, among the above-mentioned allylene sulfide groups consisting of allylene groups, two or more different combinations can be used, and among them, the combination containing the p-phenylene sulfide group and the m-phenylene sulfide group is particularly preferably used. Be done. Among these, those containing 70 mol% or more, preferably 80 mol% or more of the p-phenylene sulfide group are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by polycondensation from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. The PAS resin used in this embodiment may be a mixture of two or more different molecular weight PAS resins.

In addition to the linear PAS resin, a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents is used to partially form a branched structure or a crosslinked structure during polycondensation. Examples thereof include a polymer obtained by heating a low molecular weight linear structure polymer at a high temperature in the presence of oxygen and the like to increase the melt viscosity by oxidative crosslinking or thermal crosslinking to improve molding processability.

The melt viscosity (310 ° C., shear rate 1200 sec ^-1 ) of the PAS resin as the substrate resin used in this embodiment is 5 to 500 Pa from the viewpoint of the balance between mechanical physical properties and fluidity, including the case of the above mixed system. -Use the one of s. 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.

The PAS resin composition of the present embodiment may contain other resin components in addition to the PAS resin as the resin component as long as the effect is not impaired. The other resin components are not particularly limited, and are, 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, and polyamideimide. Resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, liquid crystal resin, fluororesin, cyclic olefin resin (cyclic olefin polymer, cyclic olefin copolymer, etc.), thermoplasticity Examples thereof include elastomers, silicone-based polymers, and various biodegradable resins. Further, two or more kinds 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 / chemical properties, processability and the like.

[Inorganic nanotubes]
In this embodiment, the inorganic nanotubes are used for the purpose of suppressing the generation of burrs. As described above, the suppression of burr generation by the inorganic nanotubes is considered to be due to the improvement in the solidification rate due to the effect of the nucleating agent. Therefore, the generation of burrs can be suppressed even with a relatively small amount of addition. In the present embodiment, the inorganic nanotubes are limited to those that do not contain carbon atoms. Therefore, the inorganic nanotubes do not contain carbon nanotubes. The inorganic nanotube is a tubular inorganic substance having a diameter on the order of nanometers.

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.
As the aluminosilicate nanotube, halloysite nanotube or meta halloysite nanotube is preferable. Of these, halloysite nanotubes are preferable from the viewpoint of low cost and availability.
Examples of the metal sulfide nanotubes include molybdenum, tungsten, and copper sulfide nanotubes. Examples of the metal halide nanotube include nickel chloride, cadmium chloride, cadmium iodide nanotube and the like.

In the present embodiment, the average length of the inorganic nanotubes is preferably 100 nm to 20 μm, more preferably 500 nm to 15 μm, further preferably 1 to 10 μm, and particularly preferably 1 to 5 μm. .. 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 μm. Further, the aspect ratio of the inorganic nanotubes is preferably 1 to 4000, more preferably 5 to 2000.
Here, the aspect ratio of the inorganic nanotube is a numerical value obtained by dividing the length of the inorganic nanotube by the diameter of the inorganic nanotube, and a manufacturer's value (a numerical value published by the manufacturer in a catalog or the like) can be adopted.

In the PAS resin composition of the present embodiment, when the amount of the inorganic nanotube is 0.01 part by mass or more and less than 10 parts by mass and less than 0.01 part by mass with respect to 100 parts by mass of the PAS resin, the effect of suppressing the generation of burrs is obtained. If it is insufficient and the amount is 10 parts by mass or more, the mechanical properties such as the impact strength of Sharpy 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.

Among the inorganic nanotubes according to the present embodiment, examples of the halloysite nanotubes on the market include "Haloysite G (685445)" manufactured by Applied Minerals.

[Non-conductive inorganic filler]
In the present embodiment, it is preferable to include a non-conductive inorganic filler in the PAS resin composition from the viewpoint of improving the mechanical properties while ensuring the insulating property. Examples of the non-conductive inorganic filler include fibrous inorganic fillers, plate-like inorganic fillers, and powder-granular inorganic fillers, one of which may be used alone or two or more thereof may be used in combination. You may. In addition, in this specification, the term "inorganic filler" means a non-conductive inorganic filler unless it is clearly stated that it is a conductive filler.

Examples of the fibrous inorganic filler include glass fiber, whisker, wollastonite, zinc oxide fiber, titanium oxide fiber, silica fiber, silica-alumina fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, etc. Examples thereof include metal fibrous substances such as mineral fibers and titanium fibers of the above, and one or more of these can be used. Of these, glass fiber is preferable.

Examples of marketed products of glass fiber are chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 μm) manufactured by Nippon Denki Glass Co., Ltd., chopped glass fiber (CS03DE 416A, average fiber) manufactured by Owens Corning Japan GK. Diameter: 6 μm), manufactured by Nippon Electric Glass 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), Nitto Spinning Co., Ltd., modified cross section chopped strand CSG 3PA-830 (major axis 28 μm, minor axis 7 μm), Nitto Spinning Co., Ltd., modified cross section chopped strand CSG 3PL-962 (major axis 20 μm, minor axis 10 μm) And so on.

The fibrous inorganic filler may be surface-treated with various surface treatment agents such as generally known epoxy-based compounds, isocyanate-based compounds, silane-based compounds, titanate-based compounds, and fatty acids. The surface treatment can improve the adhesion with the PAS resin. The surface treatment agent may be applied to the fibrous inorganic filler in advance for surface treatment or convergence treatment before material preparation, or may be added at the same time as material preparation.

The fiber diameter of the fibrous inorganic filler is not particularly limited, but can be, for example, 5 μm or more and 30 μm or less in the initial shape (shape before melt-kneading). Here, the fiber diameter of the fibrous inorganic filler means the major axis of the fiber cross section of the fibrous inorganic filler.

Examples of the powder / granular inorganic filler include talc (granular), silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, silicate such as diatomaceous earth, iron oxide, zinc oxide, alumina (granular) and the like. Non-conductive metal oxides, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, and other nitrides such as silicon carbide, silicon nitride, boron nitride and aluminum nitride, Examples thereof include poorly soluble ion crystal particles such as calcium dioxide and barium fluoride; fillers using semiconductor materials (elemental semiconductors such as Si, Ge, Se and Te; compound semiconductors such as oxide semiconductors), and the like. One kind or two or more kinds can be used. Of these, glass beads and calcium carbonate are preferable.
Examples of products on the market for calcium carbonate include Whiten P-30 (average particle size (50% d): 5 μm) manufactured by Toyo Fine Chemicals Co., Ltd. Examples of commercially available glass beads include Potters Barotini Co., Ltd., EGB731A (average particle size (50% d): 20 μm), Potters Barotini Co., Ltd., EMB-10 (average particles). Diameter (50% d): 5 μm) and the like can be mentioned.
The powdery granular inorganic filler may be surface-treated in the same manner as the fibrous inorganic filler.

Examples of the plate-shaped inorganic filler include glass flakes, talc (plate-shaped), mica, kaolin, clay, alumina (plate-shaped), and the like, and one or more of these can be used. Of these, glass flakes and talc are preferable.
Examples of marketed glass flakes are Nippon Plate Glass Co., Ltd., REFG-108 (average particle size (50% d): 623 μm), (Nippon Plate Glass Co., Ltd., fine crack (average particle size (50%)). d): 169 μm), manufactured by Nippon Plate Glass Co., Ltd., REFG-301 (average particle diameter (50% d): 155 μm), manufactured by Nippon Plate Glass Co., Ltd., REFG-401 (average particle diameter (50% d): 310 μm) ) Etc. can be mentioned.
Examples of talc products on the market include Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd. and Tarkhan Powder PKNN manufactured by Hayashi Kasei Co., Ltd.
The plate-shaped inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.

In the present embodiment, among the above-mentioned inorganic fillers, one or more selected from the group consisting of glass fibers, glass beads, glass flakes, calcium carbonate and talc is preferable. Further, from the viewpoint of improving mechanical properties, the inorganic filler preferably contains 15 to 200 parts by mass, more preferably 25 to 150 parts by mass, and 30 to 110 parts by mass with respect to 100 parts by mass of the PAS resin. It is more preferable to include it.

As described above, the PAS resin composition of the present embodiment preferably contains a non-conductive inorganic filler, but even a conductive inorganic filler is contained within a range that does not interfere with the effects of the present embodiment. May be good. When the PAS resin composition of the present embodiment contains a conductive inorganic filler, the content of the conductive inorganic filler is measured in accordance with an amount at which the molded product can exhibit electrical insulation, specifically, IEC60093. It is preferable to use an amount that can maintain the volume resistivity of the molded product at room temperature (23 ° C.) of 1 × 10 ¹⁴ Ω · cm or more. Although the term "conductive inorganic filler" is well known to those skilled in the art, carbon-based fillers (carbon black, carbon fiber, graphite, etc.) and metal-based fillers (SUS fiber, etc.) have conductivity. It means an inorganic filler having conductivity such as a metal fiber having, a metal having conductivity or a metal oxide powder, etc.), a metal surface coating filler, and the like. In one embodiment, the content of these conductive inorganic fillers is, for example, 10% by mass or less, preferably 6% by mass or less, and further preferably 4% by mass or less, based on the total PAS resin composition of the present embodiment. .. Since the content at which the conductive inorganic filler can exhibit conductivity may differ depending on the type, shape, and conductivity of the conductive inorganic filler, the content may be higher than the above content. be.

[Other ingredients]
In the present embodiment, in addition to the above-mentioned components, known additions generally added to thermoplastic resins and thermosetting resins in order to impart desired properties according to the purpose, as long as the effects are not impaired. Agents, that is, elastomers, mold release agents, lubricants, plastics, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weather resistance stabilizers, A corrosion inhibitor or the like may be blended. Although the PAS resin composition of the present embodiment can suppress the generation of burrs, a burrs inhibitor such as an alkoxysilane compound may be used in combination if necessary.

The method for producing a molded product using the PAS resin composition of the present embodiment is not particularly limited, and a known method can be adopted. For example, the PAS resin composition of the present embodiment may be put into an extruder, melt-kneaded and pelletized, and the pellets may be put into an injection molding machine equipped with a predetermined mold and injection-molded. can.

Examples of the molded product obtained by molding the PAS resin composition of the present embodiment include electrical / electronic equipment component materials, automobile equipment component materials, chemical equipment component materials, water-related component materials, and the like. Specifically, various cooling system parts of automobiles, ignition related parts, distributor parts, various sensor parts, various actuator parts, throttle parts, power module parts, ECU parts, various connector parts, piping joints (pipe fittings), joints. And so on.
Other uses include, for example, LEDs, sensors, sockets, terminal blocks, printed circuit boards, motor parts, electrical and electronic parts such as ECU cases, lighting parts, TV parts, rice cooker parts, microwave parts, iron parts, etc. It can be used for household and office electrical product parts such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air conditioner parts.

Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to the following examples. Unless otherwise specified, commercially available raw materials were used.

[Examples 1 to 7, Comparative Examples 1 to 2]
In each Example / Comparative Example, after each raw material component shown in Table 1 is dry-blended, it is put into a twin-screw extruder having a cylinder temperature of 320 ° C. (glass fiber is added separately from the side feed portion of the extruder) and melted. It was kneaded and pelletized. In Table 1, the numerical values of each component indicate parts by mass.
The details of each raw material component used are shown below.

(1) PAS resin / PPS resin: Kureha Corporation, Fortron KPS (melt viscosity: 30 Pa · s (shear velocity: 1200 sec ^-1 , 310 ° C))

(Measurement of melt viscosity of PPS resin)
The melt viscosity of the PPS resin was measured as follows.
Using a capillary graph manufactured by Toyo Seiki Seisakusho Co., Ltd., a flat die of 1 mmφ × 20 mmL was used as a capillary, and the melt viscosity was measured at a barrel temperature of 310 ° C. and a shear rate of 1200 sec ^-1 .

(2) "Haloysite G (685445)" manufactured by Inorganic Nanotube Applied Minerals (average diameter: 50 nm, average inner diameter: 15 nm)

(3) Non-conductive inorganic filler / glass fiber: Owens Corning Japan GK, chopped strand, fiber diameter: 10.5 μm, length 3 mm

[evaluation]
The following evaluations were performed using the obtained pellets of each Example / Comparative Example.
(1) Burr length Using a disk-shaped cavity mold having a burr measuring part with a mold gap of 20 μm on the outer circumference, the cavity is at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C. Was injection-molded at the minimum pressure required for complete filling, and the burr length generated in that portion was magnified and measured with a mapping projector. The measurement results are shown in Table 1.

(2) Melt Viscosity of Resin Composition Using a capillary graph manufactured by Toyo Seiki Seisakusho Co., Ltd., using a flat die of 1 mmφ × 20 mmL as a capillary, melt viscosity (MV) at a barrel temperature of 310 ° C. and a shear rate of 1000 sec ^-1 . It was measured. The measurement results are shown in Table 1. It can be said that the fluidity is excellent when the melt viscosity is 500 Pa · s or less.

(3) Charpy impact strength A test piece (width 10 mm, thickness 4 mmt) conforming to ISO3167 was produced by injection molding at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Using this test piece, the Charpy impact strength (kJ / m ² ) was measured according to ISO179 / 1eA. The measurement results are shown in Table 1.

From Table 1, it can be seen that the generation of burrs is suppressed in Examples 1 to 7 as compared with Comparative Example 1. Further, the Charpy impact strength in Examples 1 to 7 is within the permissible range, although a slight decrease is observed as compared with Comparative Example 1. On the other hand, in Comparative Example 2 in which the inorganic nanotubes were excessively added, it can be seen that the generation of burrs was suppressed, but the Charpy impact strength was significantly reduced.
From the above, it can be seen that by adding a predetermined amount of inorganic nanotubes to the PAS resin composition, it is possible to suppress the generation of burrs and suppress the decrease in Charpy impact strength.

Claims (5)

Inorganic nanotubes (limited to those containing no carbon atom) were added to 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 5 to 500 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1200 sec ^-1 . A polyarylene sulfide resin composition containing 01 parts by mass or more and less than 10 parts by mass. The polyarylene sulfide resin composition according to claim 1, wherein the inorganic nanotube is one selected from the group consisting of aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes. .. The polyarylene sulfate resin composition according to claim 2, wherein the aluminosilicate nanotube is a halloysite nanotube or a meta halloysite nanotube. The invention according to any one of claims 1 to 3, further comprising 5 to 250 parts by mass of a non-conductive inorganic filler (excluding the inorganic nanotubes) with respect to 100 parts by mass of the polyarylene sulfide resin. Polyallylensulfide resin composition. The polyarylene sulfide resin composition according to claim 4, wherein the non-conductive inorganic filler is one or more selected from the group consisting of glass fibers, glass beads, glass flakes, calcium carbonate and talc.