JP6387211B1 - Polyarylene sulfide resin composition - Google Patents

Abstract

Provided is a PAS resin composition capable of reducing burrs in a system in which an elastomer and carbon black are used in combination.
100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 40 to 180 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ , 10 to 80 parts by mass of a filler, 2 to 16 parts by mass of an elastomer, and a pH of 5 or less. 0.2 to 2.5 parts by mass of carbon black, and the amount (parts by mass) of the filler relative to 100 parts by mass of the polyarylene sulfide resin is x, the temperature of the polyarylene sulfide resin is 310 ° C., and the shear rate is 1216 sec ^{− 1} is a polyarylene sulfide resin composition in which x and y satisfy the following formula (1), where y is the melt viscosity (Pa · s) measured in ¹ .
y ≦ −1.087x + 216.96 (1)

Description

  The present invention relates to a polyarylene sulfide resin composition.

  Polyarylene sulfide (hereinafter also referred to as “PAS”) resin, represented by polyphenylene sulfide (hereinafter also referred to as “PPS”) resin, has high heat resistance, mechanical properties, chemical resistance and dimensional stability. And flame retardancy. For this reason, PAS resin is widely used for electrical / electronic equipment component materials, automotive equipment component materials, chemical equipment component materials, and the like, and is particularly used for applications with a high use environment temperature.

  The PAS resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy, but has poor toughness and is fragile. Therefore, in general, PAS resin is often used as a composite material (resin composition) to which a filler such as glass fiber is added, and the mechanical strength such as toughness is improved by adding the filler. it is conceivable that.

  On the other hand, when the PAS resin or the composition thereof is molded by injection molding or the like, burrs are easily generated. A burr | flash means the part which the molding material flowed out to the clearance gap between metal mold | dies and solidified. It is necessary to remove burrs that have solidified into a thin film or flakes and adhered to the molded product in the finishing process. Further, depending on the product shape, this finishing takes a lot of labor and cost.

  In Patent Document 1, for the purpose of providing a PAS resin composition with improved burr generation at the time of molding, a carbon-based material having a DBP oil absorption of 50 ml / 100 g or more is melt-kneaded and dispersed in a specific PAS resin in advance. It has been proposed to blend the resin composition.

Japanese Patent Application Laid-Open No. 9-1000041

An elastomer is often added to the PAS resin composition for the purpose of improving toughness and the like.
On the other hand, it is possible to reduce burrs by adding carbon black to the PAS resin composition, but if an elastomer is included in the resin composition, it may be difficult to obtain a burr reduction effect depending on the type of carbon black. It has been newly found that there is. That is, when the elastomer and carbon black are used in combination, the burr reduction effect may be difficult to obtain depending on the type of carbon black.
Then, embodiment of this invention makes it a subject to provide the PAS resin composition which can reduce a burr | flash in the system which uses an elastomer and carbon black together.

  Embodiments of the present invention relate to the following PAS resin composition.

<1> 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 40 to 180 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ , 10 to 80 parts by mass of a filler, and 2 to 16 parts by mass of an elastomer And 0.2 to 2.5 parts by mass of carbon black having a pH of 5 or less,
The amount (parts by mass) of the filler relative to 100 parts by mass of the polyarylene sulfide resin is x, and the melt viscosity (Pa · s) measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ of the polyarylene sulfide resin is y. X and y satisfy the following formula (1):
Polyarylene sulfide resin composition.
y ≦ −1.087x + 216.96 (1)
<2> The resin composition according to <1>, wherein the carbon black has an arithmetic average particle size of 10 to 15 nm.
<3> The resin composition according to <1> or <2>, wherein the polyarylene sulfide resin includes a polyphenylene sulfide resin.
<4> An olefin copolymer in which the elastomer has at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and a vinyl group. The resin composition according to any one of <1> to <3>, comprising a polymer.
<5> The resin composition according to any one of <1> to <4>, wherein the filler includes glass fibers.

  According to the embodiment of the present invention, it is possible to provide a PAS resin composition capable of reducing burrs in a system in which an elastomer and carbon black are used in combination.

The example of the relationship between content (mass part) of the filler with respect to 100 mass parts of PAS resin, and the melt viscosity (Pa * s) measured by the temperature of 310 degreeC and the shear rate of 1216 sec < ^-1 > of a PAS resin is shown roughly. It is a graph.

Preferred embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.
The PAS resin composition according to the embodiment of the present invention includes at least a polyarylene sulfide resin, a filler, an elastomer, and carbon black.

<Carbon black>
Carbon black is a carbon-based fine particle. As the carbon black, carbon black having a pH of 5 or less is used.
It is possible to reduce burrs by adding carbon black to a composition containing a PAS resin, but if an elastomer is included in the resin composition, it may be difficult to obtain a burr reduction effect depending on the type of carbon black. There is. However, when carbon black having a pH of 5 or less is used, a burr reduction effect is exhibited even if the resin composition contains an elastomer, coupled with satisfying a specific relationship regarding the melt viscosity of the PAS resin and the filler content. be able to.
The pH of carbon black is more preferably 4.5 or less, and further preferably 4.0 or less. Moreover, the pH of carbon black is 1.0 or more, for example.
The pH of carbon black is a value obtained by measuring the pH of a mixture of carbon black and distilled water with a glass electrode pH meter in accordance with JIS K 6221.

Carbon black is not particularly limited as long as it has a pH of 5 or less. Examples of the carbon black include furnace black, thermal black, and channel black according to the manufacturing method, and gas black, oil black, acetylene black, and the like according to the raw material. Examples of conductive carbon black include ketjen black.
Carbon black having a pH of 5 or less can be obtained by a method such as oxidation treatment of carbon black with acid or heat. Specific examples of commercially available carbon black having a pH of 5 or lower include, for example, Raven 3500 manufactured by Aditya Birla, Raven 7000 manufactured by Aditya Birla, # 2650 manufactured by Mitsubishi Chemical Corporation, and # 2 manufactured by Mitsubishi Chemical Corporation. 2350 and the like.
Carbon black may be used alone or in combination of two or more.

  The arithmetic average particle diameter of carbon black is preferably 10 to 15 nm, more preferably 13 to 15 nm, from the viewpoint of the balance between the black color tone and the burr suppressing effect. When the arithmetic average particle diameter of carbon black is 10 nm or more, the black color tone is excellent, and when it is 15 nm or less, the burr suppression is excellent. The arithmetic average particle diameter of carbon black is an arithmetic average diameter obtained by observing 1000 carbon black particles with an electron microscope.

The nitrogen adsorption specific surface area (NSA) of carbon black is not particularly limited, but is preferably 160 to 600 m ² / g. The nitrogen adsorption specific surface area of carbon black is a specific surface area determined by the S-BET formula from the nitrogen adsorption amount in JIS K6217. In general, the smaller the particle size, the greater the specific surface area.
The DBP (dibutyl phthalate) absorption amount of carbon black is not particularly limited, but is preferably 45 to ²⁰⁰ cm 2/100 g. The DBP absorption amount of carbon black is the amount of DBP (dibutyl phthalate) absorbed by 100 g of carbon black, and is a value measured according to the method described in JIS K6221. In general, the more the structure is developed, the greater the DBP absorption.
The volatile content of carbon black is not particularly limited, but is preferably 7% or less. The volatile content of carbon black is the volatile (weight loss) content when carbon black is heated at 950 ° C. for 7 minutes (ratio of the volatile content to the original weight). Generally, the more surface functional groups, the more components that volatilize.

The content of carbon black having a pH of 5 or less in the PAS resin composition is 0.2 to 2.5 parts by mass with respect to 100 parts by mass of the PAS resin.
When the content of carbon black in the PAS resin composition is 0.2 parts by mass or more with respect to 100 parts by mass of the PAS resin, the resulting composition is excellent in black color tone. When the content of the carbon black in the PAS resin composition is 2.5 parts by mass or less with respect to 100 parts by mass of the PAS resin, the mechanical properties such as bending strength are excellent. The content of the carbon black in the PAS resin composition is more preferably 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the PAS resin from the viewpoint of balance of performance such as black color tone and bending strength characteristics. 0.3-2.0 mass parts is further more preferable.

<PAS resin>
The PAS resin has a repeating unit — (Ar—S) — (“Ar” represents an arylene group) as a main constituent component. As the PAS resin, a generally known PAS resin having a molecular structure can be used.

Although it does not specifically limit as an arylene group, For example, p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-biphenylene group, p , P′-diphenylene ether group, p, p′-diphenylenecarbonyl group, naphthalene group and the like.
The PAS resin may be a homopolymer consisting of only one type of repeating unit or a copolymer containing a plurality of types of repeating units.

  As the homopolymer, for example, an arylene group having a p-phenylene sulfide group as a repeating unit is preferably used. A homopolymer having a p-phenylene sulfide group as a repeating unit has high heat resistance, high strength, high rigidity, and high dimensional stability in a wide temperature range.

As the copolymer, among the above-mentioned arylene sulfide groups containing an arylene group, a combination of two or more arylene sulfide groups having different arylene groups can be used. Among these, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Further, a polymer containing a p-phenylene sulfide group in a proportion of 70 mol% or more is more preferable, and a polymer containing a proportion of 80 mol% or more is more preferable. Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.
The PAS resin may be used alone or in combination of two or more.
The PAS resin having a phenylene sulfide group is a PPS resin. As the PAS resin, a PPS resin can be preferably used.

As the PAS resin, in addition to the linear PAS resin, a small amount of a monomer such as a PAS resin having a crosslinked structure, for example, a polyhaloaromatic compound having three or more halogen substituents when polycondensation is used. In this way, polymers with partially branched structures or crosslinked structures, or low molecular weight linear structure polymers are heated at high temperatures in the presence of oxygen to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, and molding. There may also be mentioned polymers with improved processability.
As the PAS resin, a linear PAS resin and a crosslinked PAS resin may be used in combination.

  The PAS resin can be produced by a conventionally known polymerization method. A PAS resin produced by a general polymerization method is usually washed several times with water or acetone in order to remove by-product impurities and the like, and then washed with acetic acid, ammonium chloride or the like. As a result, the end of the PAS resin contains a carboxyl end group in a predetermined amount.

The melt viscosity of the PAS resin measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ is 40 to 180 Pa · s from the viewpoint of the fluidity of the PAS resin composition during molding and the dispersibility of the carbon black. Hereinafter, the melt viscosity of the PAS resin measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ is simply referred to as “PAS resin melt viscosity”.
In addition, when the fluidity of the PAS resin composition at the time of molding and the dispersibility of the carbon black in the resin composition are good, the burr reducing effect by the carbon black is more easily exhibited.

The melt viscosity of the PAS resin is more preferably 45 Pa · s or more, and further preferably 50 Pa · s or more. The melt viscosity of the PAS resin composition is more preferably 150 Pa · s or less, and further preferably 130 Pa · s or less.
The melt viscosity when two or more PAS resins are used is a numerical value for a mixture of two or more PAS resins.

  Examples of the method of bringing the melt viscosity of the PAS resin within the above range include, for example, a method of appropriately selecting and mixing a commercially available PAS resin, a silane coupling agent such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, etc. Examples thereof include a method of adjusting the melt viscosity with an additive such as a disulfide compound.

<Filler>
Carbon black having a pH of 5 or less is excluded from the filler. The filler may be either an inorganic or organic filler, or a combination thereof. In addition, any of a fibrous shape, a granular shape, and a plate shape may be used, and these can be selected according to the purpose.
Examples of fibrous fillers include glass fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, potassium titanate fibers, and metal fibers such as stainless steel, aluminum, titanium, copper, and brass. Inorganic fibrous substances such as the like. High melting point organic fiber materials such as polyamide, fluororesin, and acrylic resin can also be used.
The granular fillers include silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite, silicate, iron oxide, titanium oxide, zinc oxide, etc. Examples include metal oxides, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-like filler include mica and glass flakes.
A filler may be used individually by 1 type, or may use 2 or more types together.

The filler preferably includes glass fibers.
Although the fiber diameter of glass fiber is not specifically limited, For example, 5-20 micrometers may be sufficient. Here, the fiber diameter of glass fiber means the long diameter of the fiber cross section of glass fiber.

  The cross-sectional shape of the glass fiber may be, for example, a perfect circle or an ellipse. Moreover, it does not specifically limit about the kind of glass fiber, For example, although A glass, C glass, E glass, etc. can be used, it is preferable to use E glass (non-alkali glass) among them. Further, the glass fiber may be subjected to surface treatment or not. Examples of the surface treatment for glass fiber include treatment with a coating agent such as epoxy, acrylic, urethane, or a sizing agent, and treatment with a silane coupling agent such as aminosilane or epoxysilane.

  Moreover, it is preferable to use glass fiber normally as a chopped strand (chopped glass fiber) obtained by cutting a number of these fibers into a predetermined length. In addition, it does not specifically limit about the cut length of a chopped glass fiber, For example, it can be set as about 1-10 mm.

The content of the filler in the PAS resin composition is 100 parts by mass of PAS resin from the viewpoint of fluidity at the time of molding the PAS resin composition, dispersibility of carbon black, and mechanical properties of the PAS resin composition. It is 10-80 mass parts with respect to.
By making content of a filler into 10 mass parts or more, the dispersibility of carbon black and the mechanical physical property of a PAS resin composition can be improved. Moreover, it can prevent that the fluidity | liquidity of a PAS resin composition falls too much by setting it as 80 mass parts or less.
The filler content relative to 100 parts by mass of the PAS resin is more preferably 20 parts by mass or more. Further, the content of the filler with respect to 100 parts by mass of the PAS resin is more preferably less than 65 parts by mass.

When the content of the filler increases, the fluidity at the time of molding the PAS resin composition tends to decrease. Moreover, when the melt viscosity of PAS resin becomes high, there exists a tendency for the fluidity | liquidity at the time of shaping | molding of a PAS resin composition to become low. Therefore, in order to obtain good fluidity of the resin composition at the time of molding, it is more preferable to balance the melt viscosity of the PAS resin and the amount of the filler.
From this viewpoint, in this embodiment, the filler content and the melt viscosity of the PAS resin are such that the melt viscosity of the PAS resin is 40 to 180 Pa · s, and the content of the filler in the PAS resin composition is It is 10-80 mass parts with respect to 100 mass parts of PAS resin, and satisfy | fills following formula (1). In the following formula (1), x represents the filler content (parts by mass) with respect to 100 parts by mass of the PAS resin, and y represents the melt viscosity (Pa · s) of the PAS resin.
y ≦ −1.087x + 216.96 (1)

  In other words, the melt viscosity of the PAS resin, and the content of the filler in the PAS resin composition is such that the x-axis represents the filler content (parts by mass) relative to 100 parts by mass of the PAS resin. In a graph with (Pa · s) as the y-axis, x = 10 (parts by mass), x = 80 (parts by mass), y = 40 (Pa · s), y = 180 (Pa · s) s) and y = −1.087x + 216.96 (hereinafter also referred to as “straight line 1”). The straight line of x = 10 (part by mass) intersects the straight line of y = 40 (Pa · s) at the point A where x = 10 and y = 40, and y = 180 at the point B where x = 10 and y = 180. Crosses the straight line (Pa · s). The straight line y = 180 (Pa · s) intersects the straight line 1 at a point C where x = about 34 (parts by mass) and y = 180 (Pa · s). The straight line of x = 80 (mass part) intersects with the straight line 1 at the point D of x = 80 (mass part) and y = 130 (Pa · s), and the x = 80 and y = 40 (Pa · s). At the point E, it intersects with a straight line of y = 40 (Pa · s). Therefore, the range of the pentagon is, in other words, the straight line connecting point A and point B, the straight line connecting point B and point C, the straight line connecting point C and point D, and the point D and point A pentagon formed by a straight line connecting E and a straight line connecting points E and A. FIG. 1 is a schematic graph for explaining this pentagon. The x-axis represents the filler content (parts by mass) relative to 100 parts by mass of the PAS resin, and the y-axis represents the melt viscosity (Pa · s) of the PAS resin. Where x = 10 (part by mass), x = 80 (part by mass), y = 40 (Pa · s), y = 180 (Pa · s), and straight line 1 A range of a pentagon surrounded by, and points A to E are schematically shown. And when the melt viscosity of the PAS resin and the content of the filler in the PAS resin composition are within the pentagonal range shown in FIG. 1, the fluidity of the PAS resin composition during molding and the resin composition The dispersibility of the carbon black becomes good, and the burr reduction effect can be sufficiently exhibited in combination with the carbon black having a pH of 5 or lower. FIG. 1 is a schematic graph for explanation, and is not intended to show each straight line and point accurately.

<Elastomer>
Although it does not specifically limit as an elastomer, For example, an olefin type copolymer is mentioned. An elastomer can be used individually by 1 type or in combination of 2 or more types.
When an elastomer is added, since the melt viscosity of the resin composition tends to increase, the burrs tend to be shorter than before the elastomer is added. On the other hand, when an elastomer is included, it may be difficult to obtain a burr reduction effect by carbon black. However, by using carbon black having a pH of 5 or less and satisfying a specific relationship regarding the melt viscosity of the PAS resin and the content of the filler, even if an elastomer is contained in the PAS resin composition, the burr reduction effect Can be demonstrated.

As the olefin-based copolymer, an olefin-based copolymer having at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and a vinyl group A copolymer is preferred.
The epoxy group-containing olefin copolymer is preferably an olefin copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid.

  The olefin copolymer can further contain a constituent unit derived from another copolymer component, if necessary. For example, the olefin copolymer preferably includes a structural unit derived from a (meth) acrylic acid ester in addition to the above structural unit. Hereinafter, (meth) acrylic acid ester is also referred to as (meth) acrylate. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In this specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid, and “(meth) acrylate” means both acrylate and methacrylate.

  The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene, and ethylene is particularly preferable. The α-olefin can be used alone or in combination of two or more. When the olefin copolymer contains a structural unit derived from α-olefin, flexibility is easily imparted to a molded product formed using the polyarylene sulfide resin composition. When the molded product has flexibility, it is easy to increase the bonding strength between the insert member, particularly the metal insert member and the resin member, when the insert molded product is manufactured.

  The glycidyl ester of α, β-unsaturated acid is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable. The glycidyl ester of α, β-unsaturated acid can be used alone or in combination of two or more. When the olefin copolymer contains a glycidyl ester of α, β-unsaturated acid, it is easy to increase the bonding strength between the insert member and the resin member when manufacturing an insert molded product.

  The (meth) acrylic acid ester is not particularly limited. For example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-n-hexyl, acrylic Acrylic acid esters such as acid-n-octyl; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-n-amyl, methacrylic acid And methacrylates such as -n-octyl. Of these, methyl acrylate is particularly preferable. The (meth) acrylic acid ester can be used alone or in combination of two or more. When the olefin copolymer contains a structural unit derived from a (meth) acrylic acid ester, it is easy to increase the bonding strength between the insert member and the resin member when an insert molded product is manufactured.

The epoxy group-containing olefin copolymer containing the above structural unit can be produced by performing copolymerization by a conventionally known method.
For example, the copolymer can be obtained by performing copolymerization by a generally well-known radical polymerization reaction. The type of copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Examples of the olefin copolymer include polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyacrylate-2-ethylhexyl, polystyrene, polyacrylonitrile. An olefin-based graft copolymer in which acrylonitrile / styrene copolymer, butyl acrylate / styrene copolymer, or the like is chemically bonded in a branched or cross-linked structure may be used.

More specifically, examples of the epoxy group-containing olefin copolymer include a glycidyl methacrylate-modified ethylene copolymer, a glycidyl ether-modified ethylene copolymer, and the like, and among them, a glycidyl methacrylate-modified ethylene copolymer. Is preferred.
Examples of the glycidyl methacrylate-modified ethylene copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate copolymer, and ethylene-glycidyl methacrylate-methyl acrylate copolymer. Among them, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is preferable because a particularly excellent metal resin composite molded body can be obtained. Particularly preferred. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include “Bond First (registered trademark)” (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymer and glycidyl ether-ethylene copolymer.

  The content of the elastomer in the PAS resin composition is 2 to 16 parts by mass with respect to 100 parts by mass of the PAS resin. The elastomer content relative to 100 parts by mass of the PAS resin is more preferably 2.5 parts by mass or more, and further preferably 3 parts by mass or more. Further, the content of the elastomer with respect to 100 parts by mass of the PAS resin is more preferably 14 parts by mass or less, and further preferably 12 parts by mass or less.

<Other ingredients>
The PAS resin composition may contain other resins as long as the effects of the present invention are not impaired. In addition, in order to impart desired properties to the molded product, for example, a nucleating agent, a pigment other than carbon black having a pH of 5 or less (for example, an inorganic calcined pigment), an antioxidant, a stabilizer, a plasticizer, a lubricant, a release agent Additives such as molds and flame retardants may be added. Thus, the resin composition which provided the desired characteristic is also contained in the PAS resin composition used by this invention.

<Preparation of resin composition>
The PAS resin composition can be prepared by a conventionally known method. Specifically, for example, after mixing the above-described components, a method of preparing a pellet by kneading and extruding with an extruder, once preparing a pellet having a different composition, mixing the pellet in a predetermined amount, and providing for molding, Any method such as a method of obtaining a molded product having a desired composition after molding or a method of directly charging one or more of each component into a molding machine can be suitably used.
The PAS resin composition preferably has a bending strength (FS) of 150 MPa or more. The bending strength (FS) was determined by drying a pellet of the resin composition at 140 ° C. for 3 hours, and then by injection molding, a test piece according to ISO 316 at a molding cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. (width 10 mm, thickness 4 mm ) And measured according to ISO178 using this test piece.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Examples 1-14, Comparative Examples 1-22]
<Production of PAS resin composition>
About each Example and a comparative example, the mixture obtained by dry-blending each raw material shown in Tables 1-5 was thrown into the twin-screw extruder with a cylinder temperature of 320 degreeC (a filler is separated from the side feed part of an extruder). Addition), melt-kneaded and pelletized. Details of each raw material shown in the table are shown below.

(1) PAS resin / PPS resin 1: “Fortron KPS” manufactured by Kureha Co., Ltd. (melt viscosity: 28 Pa · s (temperature 310 ° C. and shear rate 1216 sec ⁻¹ ))
PPS resin 2: “Fortron KPS” manufactured by Kureha Corporation (melt viscosity: 130 Pa · s (temperature 310 ° C. and shear rate 1216 sec ⁻¹ ))
PPS resin 3: “Fortron KPS” manufactured by Kureha Co., Ltd. (melt viscosity: 7 Pa · s (temperature 310 ° C. and shear rate 1216 sec ⁻¹ ))
PPS resin 4: “Fortron KPS” manufactured by Kureha Co., Ltd. (melt viscosity: 220 Pa · s (temperature 310 ° C. and shear rate 1216 sec ⁻¹ ))

(Measurement of melt viscosity of PAS resin)
The melt viscosity of the PAS resin was measured as follows.
Using a Capillograph manufactured by Toyo Seiki Seisakusho, a 1 mmφ × 20 mmL / flat die was used as a capillary, and the melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ was measured.
The melt viscosity of the PPS resins 1 to 4 is a value measured for each resin.
The melt viscosity of the PAS resins listed in the table is measured for a mixture of these two or more PAS resins mixed in the proportions listed in the table when two or more PAS resins are used in the composition. It is the value.

(2) Filler / glass fiber: “Chopped Strand ECS03T-747H” manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter: 10.5 μm)

(3) Elastomer
-Olefin copolymer: “Bond First (registered trademark) 7L” manufactured by Sumitomo Chemical Co., Ltd. (glycidyl methacrylate (GMA) content: 3 mass%)

(4) Carbon black
Carbon black 1 (CB1): “Raven 3500” manufactured by Aditya Birla (pH: 3-3.5, arithmetic average particle size: 13 nm, specific surface area (NSA): 375 m ² / g, DBP absorption: 105 cm ³ / 100g, volatile content: 5% by mass)
Carbon black 2 (CB2): “# 750B” manufactured by Mitsubishi Chemical Corporation (pH: 7.5, arithmetic average particle size: 22 nm, specific surface area (NSA): 124 m ² / g, DBP absorption: 116 cm ³ / 100g, volatile content: 1% by mass)
In the table, the amount of carbon black indicates the amount of carbon black containing volatile components.
The pH, arithmetic average particle diameter, specific surface area (NSA), DBP absorption amount, and volatile content of the carbon black are values measured by the method described in the section of carbon black.

(5) Mold release agent / Pentaerythritol stearate: “Unistar (registered trademark) H476” manufactured by NOF Corporation

<Evaluation>
The following evaluation was performed. The results are shown in Tables 1-5.
(1) Burr length Each resin composition pellet was injection-molded using a disk-shaped cavity mold in which a burr measuring part having a mold gap of 20 μm was provided in part on the outer periphery. The burr length generated in the part was measured with an image measuring machine and analyzed to obtain the burr length. The molding conditions were as follows, and 5 shots were molded for each and the average value was shown.
Mold temperature: 150 ° C
Cylinder temperature: 320 ° C
Injection pressure: The minimum pressure that the cavity can fill completely

(2) Melt viscosity (MV) of the composition
The melt viscosity (MV) of the PAS resin composition was measured by using a capillograph manufactured by Toyo Seiki Seisakusho, using a 1 mmφ × 20 mmL / flat die as a capillary, and measuring the melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1000 sec ⁻¹ .

(3) Bending strength (FS)
Each resin composition pellet was dried at 140 ° C. for 3 hours, and then a test piece (width 10 mm, thickness 4 mmt) according to ISO 316 was produced by injection molding at a molding cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Using this test piece, the bending strength (MPa) was measured according to ISO178.

Each of the PAS resin compositions of Examples 1 to 14 showed a shorter burr length compared to the resin composition of the comparative example.
On the other hand, in Comparative Examples 7 and 20 to 22 where the melt viscosity of the PAS resin is low, burrs having a length of 180 μm or more are generated, and in addition, in Comparative Examples 7, 20 and 22, the bending strength (FS). Were as small as 90 MPa, 125 MPa, and 107 MPa, respectively. In Comparative Examples 8 to 10, the fluidity of the PAS resin composition was low, and molding could not be performed.
Moreover, Examples 1-5 and 8-14 respectively showed short burr | length length compared with Comparative Examples 1-5 and 13-19 which differ only in the point whose pH of carbon black is larger than 5.

Claims (3)

100 parts by mass of polyarylene sulfide resin having a melt viscosity of 40 to 180 Pa · s measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ , 10 to 80 parts by mass of filler, 2 to 16 parts by mass of elastomer, and pH 1 0.2 to 2.5 parts by mass of carbon black of 0 or more and 5 or less,
The filler comprises surface-treated glass fibers ;
An olefin copolymer in which the elastomer has at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and a vinyl group; Including
The amount (parts by mass) of the filler relative to 100 parts by mass of the polyarylene sulfide resin is x, and the melt viscosity (Pa · s) measured at a temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ of the polyarylene sulfide resin is y. X and y satisfy the following formula (1):
Polyarylene sulfide resin composition.
y ≦ −1.087x + 216.96 (1)   The resin composition according to claim 1, wherein the carbon black has an arithmetic average particle size of 10 to 15 nm.   The resin composition according to claim 1 or 2, wherein the polyarylene sulfide resin includes a polyphenylene sulfide resin.

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