KR20220088326A - Polyarylene sulfide resin composition - Google Patents

Abstract

[Problem] The present invention provides a polyarylene sulfide resin composition with less burr generation.
[Solution] With respect to 100 parts by mass of 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 , inorganic nanotubes (limited to those containing no carbon atoms) .) is a polyarylene sulfide resin composition containing 0.01 parts by mass or more and less than 10 parts by mass. The inorganic nanotubes are preferably one selected from the group consisting of aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes.

Description

Polyarylene sulfide resin composition {Polyarylene sulfide resin composition}

The present invention relates to a polyarylene sulfide resin composition.

Polyarylene sulfide resin (hereinafter sometimes referred to as “PAS resin”) typified by polyphenylene sulfide resin (hereinafter sometimes referred to as “PPS resin”) has high heat resistance, mechanical properties, chemical resistance, Since it has dimensional stability and flame retardancy, it is widely used for electrical/electronic device component materials, automotive device component materials, chemical device component materials, and the like. However, the PAS resin has a problem that, since the crystallization rate is slow, the cycle time during molding is long, and burrs are frequently generated during molding.

As a method of reducing the generation of burrs, it is known to add various alkoxysilane compounds (refer to Patent Documents 1 and 2). Various alkoxysilane compounds have high reactivity with PAS resin, and the effect of improving mechanical properties and suppressing the generation of a burr, etc. are recognized. However, there is a limit to the effect of suppressing the generation of burrs, and it is not possible to sufficiently satisfy the market demand, and also does not have the effect of speeding up the crystallization rate.

In order to solve the said problem, the resin composition which mix|blended each specific amount of specific carbon nanotubes and an inorganic filler as needed with specific PAS resin is proposed (refer patent document 3). In addition, there has been proposed a resin composition comprising two PPS resins having different melt viscosities, and kaolin, attapulgite, or a mixture thereof having a predetermined average particle diameter (see Patent Document 4). ).

Japanese Patent Publication No. 6-21169 Japanese Laid-Open Patent Publication No. 1-146955 Japanese Laid-Open Patent Publication No. 2006-143827 Japanese Patent Laid-Open No. 9-157525

In the resin composition described in Patent Document 3, in order to sufficiently suppress the occurrence of burrs, it is necessary to add carbon nanotubes in a relatively large amount. Then, the resin composition has conductivity due to the conductivity of the carbon nanotubes. In addition, such a resin composition cannot be used for a molded article requiring insulation. Further, in Patent Document 4, kaolin, attapulgite, or a mixture thereof having a predetermined average particle diameter is considered to have an “effect of imparting thixotropy to the material (the effect of increasing the shear rate dependence of melt viscosity)” , it is thought that the occurrence of burrs will be significantly reduced as the melt viscosity of the material rises at once during the holding pressure process (the process in which the shear rate becomes small) in injection molding.” That is, since the 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 in fact, 10 to 150 parts by weight with respect to 100 parts by weight of the PPS resin composition. The purport that it is preferable is described. By adding inorganic fillers, such as kaolin, generation|occurrence|production of a burr can be suppressed, but there is concern that other problems, such as a moldability and a strength fall, arise by increasing the addition amount.

The present invention has been made in view of the above conventional problems, and an object of the present invention is to provide a polyarylene sulfide resin composition with less burr generation.

One aspect of the present invention that solves the above problems is as follows.

(1) Inorganic nanotubes (limited to those containing no carbon atoms) 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 . ) of 0.01 parts by mass or more and less than 10 parts by mass, the polyarylene sulfide resin composition.

(2) In the above (1), wherein the inorganic nanotubes are one selected from the group consisting of aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, and metal halide nanotubes A polyarylene sulfide resin composition as described.

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

(4) Any one of (1) to (3) above, 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 The polyarylene sulfide resin composition as described in one.

(5) The polyarylene sulfide resin composition according to (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.

ADVANTAGE OF THE INVENTION According to this invention, the polyarylene sulfide resin composition with little generation|occurrence|production of a burr can be provided.

The polyarylene ^sulfide resin composition of this embodiment contains inorganic nanotubes (provided, It is limited to the thing which does not contain a carbon atom.) 0.01 mass part or more and less than 10 mass parts are included.

The PAS resin composition of this embodiment suppresses generation|occurrence|production of a burr by including an inorganic nanotube. It is estimated that the improvement of the crystallization rate (improvement of the solidification rate by the nucleating agent effect) contributes to the mechanism by which the burr is suppressed by the addition of inorganic nanotubes. Further, by improving the crystallization rate, it is possible to shorten the molding cycle. In addition, many inorganic nanotubes generally have insulating properties, and when inorganic nanotubes having insulating properties are used, the insulating properties of the PAS resin composition do not decrease. In this respect, it is different from using carbon nanotubes.

Hereinafter, each component of the PAS resin composition of this embodiment is demonstrated.

[Polyarylene sulfide resin]

PAS resin has excellent mechanical properties, electrical properties, heat resistance and other physical and chemical properties, and also has good processability.

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

Examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p,p′-diphenylenesulfone group, p,p′-biphenylene group, p,p '-diphenylene ether group, p,p'-diphenylenecarbonyl group, naphthalene group, etc. are mentioned. The PAS resin may be a homopolymer composed of only the above repeating units, and in some cases, a copolymer containing the following heterogeneous repeating units is 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 a p-phenylene sulfide group as a repeating unit is preferably used. In addition, as the copolymer, a combination of two or more different types can be used among the arylene sulfide groups comprising an arylene group. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. do.

Among these, those containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide groups, are suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. In addition, among these PAS resins, a substantially linear high molecular weight polymer obtained by polycondensation from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. In addition, you may mix and use the PAS resin of 2 or more types of different molecular weight PAS resin used by this embodiment.

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 three or more halogen substituents during polycondensation can be mentioned. . Further, a polymer having improved moldability by heating a low molecular weight linear polymer in the presence of oxygen or the like at a high temperature to increase the melt viscosity by oxidative crosslinking or thermal crosslinking can also be mentioned.

The melt viscosity (310 ° C., shear rate 1200 sec ^-1 ) of the PAS resin as the base resin used in this embodiment is 5 to 500 Pa·s is used. The melt viscosity of the PAS resin is preferably 7 to 300 Pa·s, more preferably 10 to 250 Pa·s, and particularly preferably 13 to 200 Pa·s.

In addition, in addition to PAS resin, the PAS resin composition of this embodiment may contain other resin components as a resin component in the range which does not impair the effect. There is no limitation in particular as another resin component, 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, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, liquid crystal resin, fluororesin, cyclic olefin resin (cyclic olefin polymers, cyclic olefin copolymers, etc.), thermoplastic elastomers, silicone polymers, and various biodegradable resins. Moreover, you may use together 2 or more types of resin components. 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.

[Inorganic Nanotubes]

In this embodiment, inorganic nanotubes are used for the purpose of suppressing burr generation. As mentioned above, suppression of burr generation by an inorganic nanotube is thought to originate in the solidification rate improvement by the nucleating agent effect. Therefore, even a relatively small amount of addition can suppress the occurrence of burrs. Also, in the present embodiment, the inorganic nanotubes are limited to those containing no carbon atoms. Accordingly, inorganic nanotubes do not include carbon nanotubes. In addition, the inorganic nanotube is a tubular inorganic material having a diameter of 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 nanotubes, halloysite nanotubes or meta halloysite nanotubes are preferable. Among them, halloysite nanotubes are preferable from the viewpoints of low cost and availability.

Further, examples of the metal sulfide nanotubes include molybdenum, tungsten, or copper sulfide nanotubes. Nickel chloride, cadmium chloride, or cadmium iodide nanotube etc. are mentioned as a metal halide nanotube.

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, still more preferably 1 to 10 μm, particularly preferably 1 to 5 μm. do. Moreover, it is preferable that it is 5-100 nm, and, as for the average outer diameter of an inorganic nanotube, it is more preferable that it is 10-80 nm, It is more preferable that it is 30-70 nm. Moreover, 1-4000 are preferable and, as for the aspect-ratio of an inorganic nanotube, 5-2000 are more preferable.

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 value (a numerical value published by a manufacturer in a catalog or the like) can be employed.

In the PAS resin composition of the present embodiment, 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes are included with respect to 100 parts by mass of the PAS resin. If it is negative or more, for example, mechanical properties such as Charpy impact strength tend to deteriorate. Content of an inorganic nanotube becomes like this. Preferably it is 0.5-9.9 mass parts, More preferably, it is 1.0-9.5 mass parts.

Among the inorganic nanotubes according to the present embodiment, commercially available halloysite nanotubes include "Haloisite G (685445)" manufactured by Applied Minerals Co., Ltd., and the like.

[Non-conductive inorganic filler]

In this embodiment, it is preferable to contain a nonelectroconductive inorganic filler in a PAS resin composition from a viewpoint of aiming at the improvement of mechanical properties, ensuring insulation. As a nonelectroconductive inorganic filler, a fibrous inorganic filler, a plate-shaped inorganic filler, and a granular inorganic filler are mentioned, 1 type may be used individually among these, and 2 or more types may be used together. In addition, in this specification, when it describes with an "inorganic filler", unless it specifies that it is an electrically conductive filler, a nonelectroconductive inorganic filler is meant.

Examples of the fibrous inorganic filler include minerals such as glass fiber, whisker, wollastonite, zinc oxide fiber, titanium oxide fiber, silica fiber, silica-alumina fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and potassium titanate fiber. and metal fibrous substances such as fibers and titanium fibers, and one or two or more thereof may be used. Among them, glass fiber is preferable.

Examples of commercially available glass fiber products include chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 µm), manufactured by Nippon Denki Glass Co., Ltd., and chopped glass fiber (CS03DE 416A, average fiber diameter), manufactured by Owens Corning Japan Co., Ltd. : 6㎛), Nippon Denki Glass Co., Ltd., chopped glass fiber (ECS03T-747H, average fiber diameter: 10.5 μm), Nippon Denki Glass Co., Ltd., chopped glass fiber (ECS03T-747, average fiber diameter) : 13 μm), Nitto Spinning Co., Ltd., CSG 3PA-830 (long diameter 28 μm, minor diameter 7 μm), modified cross-section chopped strand CSG 3PL-962 (long diameter 20 μm, minor diameter of 10 µm) and the like.

The fibrous inorganic filler may be surface-treated with various surface treatment agents, such as a generally known epoxy-based compound, isocyanate-based compound, silane-based compound, titanate-based compound, and fatty acid. Adhesiveness with PAS resin can be improved by surface treatment. A surface treatment agent may be previously applied to a fibrous inorganic filler before material preparation to give a surface treatment or a convergence treatment, or may be added simultaneously at the time of material preparation.

Although the fiber diameter of a fibrous inorganic filler is not specifically limited, WHEREIN: In an initial shape (shape before melt-kneading), it can be 5 micrometers or more and 30 micrometers or less, for example. Here, the fiber diameter of a fibrous inorganic filler means the long diameter of the fiber cross section of a fibrous inorganic filler.

Examples of the particulate inorganic filler include talc (granular), silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, silicates such as diatomaceous earth, iron oxide, zinc oxide, and alumina (granular) metal oxides that do not have electrical conductivity. , metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other nitrides such as silicon carbide, silicon nitride, boron nitride, aluminum nitride, calcium fluoride, barium fluoride, etc.; and fillers using semiconductor materials (elementary semiconductors such as Si, Ge, Se, and Te; compound semiconductors such as oxide semiconductors, etc.), and these may be used alone or in combination of two or more. Among them, glass beads and calcium carbonate are preferable.

As an example of the commercial item of calcium carbonate, Toyo Fine Chemicals Co., Ltd. product, Phyton P-30 (average particle diameter (50% d): 5 micrometers), etc. are mentioned. Moreover, as an example of a commercial item of glass beads, Porters Barottini Co., Ltd. product, EGB731A (average particle diameter (50% d): 20 micrometers), Porters Balotini Co., Ltd. product, EMB-10 (average particle diameter ( 50% d): 5 µm) and the like.

The granular inorganic filler may also be surface-treated similarly to the fibrous inorganic filler.

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

As an example of the commercial item of glass flakes, Nihon Itagarasu Co., Ltd. product, REFG-108 (average particle diameter (50%d): 623 micrometers), (Nippon Itagalas Co., Ltd. product, fine flakes (average particle diameter (50%)) d): 169 µm), manufactured by Nippon Itagas Co., Ltd., REFG-301 (average particle size (50% d): 155 µm), manufactured by Nippon Itagas, REFG-401 (average particle size (50%)) d): 310 µm) and the like.

As an example of the commercial item of a talc, the Matsumura Sangyo Co., Ltd. product Crown Talc PP, Hayashi Kasei Co., Ltd. product talcan powder PKNN, etc. are mentioned.

The plate-shaped inorganic filler may also be surface-treated similarly to the fibrous inorganic filler.

In this embodiment, among the above inorganic fillers, it is preferable that it is 1 type(s) or 2 or more types chosen from the group which consists of glass fiber, glass bead, glass flake, calcium carbonate, and a talc. In addition, from the viewpoint of improving mechanical properties, the inorganic filler (however, excluding inorganic nanotubes) is preferably contained in an amount of 5 to 250 parts by mass, and 15 to 200 parts by mass based on 100 parts by mass of the PAS resin. It is more preferable, it is still more preferable to contain 25-150 mass parts, It is especially preferable to contain 30-110 mass parts.

As mentioned above, although it is preferable that a nonelectroconductive inorganic filler is included in the PAS resin composition of this embodiment, even if it is an electrically conductive inorganic filler, you may contain it in the range which does not impair the effect of this embodiment. When the PAS resin composition of the present embodiment contains an electrically conductive inorganic filler, the content of the electrically conductive inorganic filler is an amount capable of exhibiting electrical insulation in the molded article, specifically, room temperature (23 ° C.) of the molded article measured in accordance with IEC60093 It is preferable to use it in an amount which can maintain the volume resistivity in 1x10 ¹⁴ Ω·cm or more. In addition, although the term "conductive inorganic filler" is well known to those skilled in the art, carbon-based fillers (carbon black, carbon fiber, graphite, etc.), metal-based fillers (metal fibers having conductivity such as SUS fiber, metal or metal oxide having conductivity) powder, etc.), means an inorganic filler having conductivity, such as a metal surface coating filler. In one embodiment, content of these electroconductive inorganic fillers is 10 mass % or less of the whole PAS resin composition of this embodiment, for example, 6 mass % or less is preferable, and 4 mass % or less is more preferable. In addition, since the content which can express electroconductivity of an electrically conductive inorganic filler may differ also with the kind, shape, and electroconductivity of an electrically conductive inorganic filler, it may be more than the said content in some cases.

[Other Ingredients]

In this embodiment, in the range which does not impair the effect, in addition to each said component, in order to provide the desired characteristic according to the objective, you may mix|blend well-known additives generally added to a thermoplastic resin and a thermosetting resin. Examples of the additive include elastomers, mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weathering stabilizers, and corrosion inhibitors. Moreover, although the PAS resin composition of this embodiment can suppress generation|occurrence|production of a burr by itself, you may use together burr inhibitors, such as an alkoxysilane compound, as needed.

There is no limitation in particular as a method of producing a molded article using the PAS resin composition of this embodiment, A well-known method is employable. For example, it can produce by injecting|throwing-in the PAS resin composition of this embodiment to an extruder, melt-kneading, and pelletizing, inject|throwing-in this pellet to the injection molding machine provided with a predetermined|prescribed metal mold|die, and injection-molding.

As a molded article formed by shape|molding the PAS resin composition of this embodiment, an electric/electronic device component material, automobile device component material, chemical device component material, kitchen/bathroom/toilet related component material, etc. are mentioned. Specifically, various automotive cooling system parts, ignition-related parts, distributor parts, various sensor parts, various actuator parts, throttle parts, power module parts, ECU parts, various connector parts, piping connections (pipe connection), joints, etc. can

In addition, as other uses, for example, electric/electronic parts such as LEDs, sensors, sockets, terminal blocks, printed circuit boards, motor parts, ECU cases, lighting parts, television parts, rice cooker parts, microwave oven parts, iron parts, It can be used for parts of home and office electric appliances such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air conditioner parts.

Example

Hereinafter, although an Example demonstrates this embodiment more concretely, this embodiment is not limited to a following Example. In addition, unless otherwise indicated, a commercial item was used as a raw material.

[Examples 1-7, Comparative Examples 1-2]

In each Example and Comparative Example, after dry blending each raw material component shown in Table 1, it was put into a twin-screw extruder at a cylinder temperature of 320°C (glass fiber is added separately from the side feed part of the twin-screw extruder), and melted It was kneaded and pelletized. In addition, in Table 1, the numerical value of each component shows a mass part.

In addition, the detail of each raw material component used is shown below.

(1) PAS resin

ㆍPSS resin: Made by Creha Co., Ltd., Potron KPS (melt viscosity: 30 Pa·s (shear rate: 1200 sec ^-1 , 310°C))

(Measurement of melt viscosity of PPS resin)

The melt viscosity of the PPS resin was measured as follows.

Melt viscosity was measured at a barrel temperature of 310°C and a shear rate of 1200 sec ⁻¹ using a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. and a flat die of 1 mm φ ×20 mmL as a capillary tube.

(2) inorganic nanotubes

ㆍApplied Minerals Co., Ltd., "Halloysite G (685445)" (average diameter: 50 nm, average inner diameter: 15 nm)

(3) non-conductive inorganic fillers

ㆍGlass fiber: made by Owens Corning Japan Co., Ltd., chopped strand, fiber diameter: 10.5㎛, length 3mm

[evaluation]

The following evaluation was performed using the obtained pellets of each Example and Comparative Example.

(1) burr length

Using a mold of a disc-shaped cavity in which a burr measuring part having a mold gap of 20 µm in part is installed on the outer periphery, injection molding is performed at a cylinder temperature of 320 °C and a mold temperature of 150 °C at the minimum pressure required to completely fill the cavity, and the part The length of the burr on the burr was measured by magnifying it with a mapper. Table 1 shows the measurement results.

(2) melt viscosity of resin composition

Melt viscosity (MV) was measured at a barrel temperature of 310° C. and a shear rate of 1000 sec ⁻¹ using a capillary made by Toyo Seiki Seisakusho Co., Ltd., using a flat die of 1 mm ϕ ×20 mmL as a capillary tube. A measurement result is shown in Table 1. When the melt viscosity is 500 Pa·s or less, it can be said that the fluidity is excellent.

(3) Charpy impact strength

In injection molding, a test piece (width 10 mm, thickness 4 mmt) conforming to ISO3167 was prepared 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. Table 1 shows the measurement results.

From Table 1, it can be seen that in Examples 1 to 7, the generation of burrs was suppressed as compared with Comparative Example 1. In addition, although the Charpy impact strength in Examples 1-7 shows a slight fall compared with the comparative example 1, it is within an allowable range. On the other hand, in Comparative Example 2 in which an excessive amount of inorganic nanotubes was added, it can be seen that although generation of burrs was suppressed, the Charpy impact strength was remarkably reduced.

From the above, it turns out that by adding a predetermined amount of inorganic nanotubes to a PAS resin composition, generation|occurrence|production of a burr can be suppressed and the fall of the Charpy impact strength can be suppressed.

Claims (5)

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 , 0.01 inorganic nanotubes (limited to those containing no carbon atoms) A polyarylene sulfide resin composition comprising not less than 10 parts by mass and less than 10 parts by mass. The method of claim 1,
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, polyarylene sulfide resin composition. . 3. The method of claim 2,
The polyarylene sulfide resin composition, wherein the aluminosilicate nanotube is a halloysite nanotube or a meta halloysite nanotube. 4. The method according to any one of claims 1 to 3,
Based on 100 parts by mass of the polyarylene sulfide resin, the polyarylene sulfide resin composition further comprising 5 to 250 parts by mass of a non-conductive inorganic filler (however, excluding the inorganic nanotubes). 5. The method of claim 4,
The polyarylene sulfide resin composition 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.