WO2018198850A1

WO2018198850A1 - Poly(arylene sulfide) resin composition and insert-molded article

Info

Publication number: WO2018198850A1
Application number: PCT/JP2018/015670
Authority: WO
Inventors: 大西　克平; 竜也金塚
Original assignee: ポリプラスチックス株式会社
Priority date: 2017-04-27
Filing date: 2018-04-16
Publication date: 2018-11-01
Also published as: JP2020109135A

Abstract

[Problem] To provide a poly(arylene sulfide) resin composition and an insert-molded article using the resin composition which exhibit excellent impact resistance at high and low temperatures and low warpage. [Solution] This poly(arylene sulfide) resin composition contains a poly(arylene sulfide) resin A, a fibrous inorganic filler B1 having an aspect ratio, which is the ratio between the major axis and the minor axis of a cross section perpendicular to the longitudinal direction, of 3.0 or more, a non-fibrous inorganic filler B2, and an olefin copolymer C containing constituent units derived from an α-olefin and constituent units derived from a glycidyl ester of an α,β-unsaturated acid. The mass ratio B1/B2 of the fibrous inorganic filler B1 and the non-fibrous inorganic filler B2 is more than 1.0. The poly(arylene sulfide) resin composition contains a fibrous inorganic filler B3 in an amount of no more than 50 parts by mass relative to 100 parts by mass of the poly(arylene sulfide) resin A, the fibrous inorganic filler B3 having an aspect ratio, which is the ratio between the major axis and the minor axis of a cross section perpendicular to the longitudinal direction, of 2.0 or less.

Description

Polyarylene sulfide-based resin composition and insert molded product

The present invention relates to a polyarylene sulfide-based resin composition and an insert molded product.

An insert molded product is a molded product obtained by integrally molding an insert member made of a metal, an inorganic solid, or the like and a resin member made of a thermoplastic resin composition, and is widely used for automobile parts, electric / electronic parts, OA equipment parts, and the like. Applied to the field. However, the metal forming the insert molded product and the thermoplastic resin composition are greatly different in thermal expansion coefficient and shrinkage rate due to temperature change, and the insert molded product may be destroyed due to temperature change during use. . Therefore, high-low temperature impact resistance (heat shock resistance) is required for insert molded products.

Polyarylene sulfide resin is known as a resin having relatively high high-temperature impact resistance among thermoplastic resins. However, since polyarylene sulfide-based resins have poor toughness and are fragile, the structure of the insert member is complicated and the thickness of the resin member does not change, for example, parts such as power modules and reactors used in hybrid cars. When there is a large portion, or when the change in the high and low temperature of the environment in which it is used is large, such as parts around the engine of an automobile, the high and low temperature impact resistance may be reduced. As a method for solving these problems, there is a technique of blending a polyarylene sulfide-based resin with a fibrous filler having a flat cross-sectional shape (Patent Document 1).

Further, since the polyarylene sulfide-based resin is a crystalline resin, it has a so-called shrinkage rate anisotropy in which the shrinkage rate of the resin in the cooling process is different between the flow direction of the resin and the direction perpendicular thereto. Due to the anisotropy of the shrinkage rate, warpage and sink may occur in the obtained insert molded product, and the dimensional accuracy may be lowered. As a method for suppressing the occurrence of sink marks, a fibrous reinforcing agent having a flat cross-sectional shape is added to a substantially linear polyarylene sulfide resin having a specific Na content and a resin pH in a specific range. There is a technique of blending (Patent Document 2).
Japanese Patent Laid-Open No. 2005-161693 JP 2006-328291 A

An object of the present invention is to provide a polyarylene sulfide-based resin composition excellent in high-temperature impact properties and low warpage and an insert molded product using the resin composition.

In the course of research, the present inventor combined a fibrous inorganic filler having a predetermined different diameter ratio and a non-fibrous inorganic filler in a predetermined ratio as an inorganic filler to be blended with the polyarylene sulfide resin. Thus, even when the resin composition is used for a resin member of an insert-molded product having a structure in which the high and low temperature impact properties are likely to be lowered, it is found that the superior high and low temperature impact properties can be achieved, and the present invention is completed. It came.

That is, the polyarylene sulfide-based resin composition according to the present invention is a polyarylene sulfide-based resin A, a fibrous material having a different diameter ratio of 3.0 or more, which is a ratio of a major axis to a minor axis of a cross section perpendicular to the longitudinal direction. An inorganic filler B1, a non-fibrous inorganic filler B2, and an olefin copolymer C containing a structural unit derived from α-olefin and a structural unit derived from a glycidyl ester of α, β-unsaturated acid, The mass ratio B1 / B2 of the fibrous inorganic filler B1 and the non-fibrous inorganic filler B2 exceeds 1.0, and the different diameter ratio which is the ratio of the major axis to the minor axis of the cross section perpendicular to the longitudinal direction is 2.0. The content of the fibrous inorganic filler B3 as described below is 50 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A.

In the present invention, the content of the fibrous inorganic filler B1 is preferably 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A. Moreover, it is preferable that content of non-fibrous inorganic filler B2 is 20 to 60 mass parts with respect to 100 mass parts of polyarylene sulfide-type resin A.

In the present invention, the average particle diameter of the non-fibrous inorganic filler B2 is preferably 10 μm or more. Moreover, it is preferable that non-fibrous inorganic filler B2 contains a granular inorganic filler. The particulate inorganic filler preferably contains either or both of calcium carbonate and glass beads.

In the present invention, the content of the olefin copolymer C is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A. More preferably, they are 5 to 30 mass parts.

In the present invention, it is preferable that the fibrous inorganic filler B3 is not substantially contained.

An insert-molded article according to the present invention has an insert member formed using a metal, an alloy, or an inorganic solid material, and a resin member that covers at least a part of the surface of the insert member, and the resin member is the polyarylene sulfide. It is characterized by being formed using a system resin composition.

In the present invention, the resin member has either or both of a weld part where flow ends of the resin composition are joined and a stress concentration part where stress generated by expansion and contraction concentrates, and the weld part and / or stress. It can comprise so that the thickness of the at least one part area | region of a concentration part may be 2 mm or less.

According to the present invention, it is possible to provide a polyarylene sulfide-based resin composition excellent in high-low temperature impact property and low warpage property and an insert molded product using the resin composition.

It is a figure which shows typically the test piece (insert molding product) used by the high-temperature impact test, Comprising: (a) is a perspective view, (b) is a top view. It is a figure which shows the insert member of the insert molded product shown in FIG. 1, Comprising: (a) is a perspective view, (b) is an enlarged plan view of an acute angle shape part. It is explanatory drawing about the dimension (mm) of the test piece shown in FIG. 1, Comprising: (a) is a top view, (b) is a side view. It is explanatory drawing about the measurement position of low curvature property.

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[Polyarylene sulfide-based resin composition]
The polyarylene sulfide-based resin composition (hereinafter also simply referred to as “resin composition”) is a resin composition containing a resin having a polyarylene sulfide-based resin as a main component. “Main component” means 80% by mass or more, 85% by mass or more, and 90% by mass or more in the resin component. The resin composition according to the present embodiment comprises a polyarylene sulfide-based resin A, a fibrous inorganic filler B1, a non-fibrous inorganic filler B2, and an olefin copolymer C having a different diameter ratio of 3.0 or more. contains.

(Polyarylene sulfide resin A)
The polyarylene sulfide-based resin A is a resin having a repeating unit represented by the following general formula (I).
-(Ar-S)-(I)
(However, Ar represents an arylene group.)

The arylene group is not particularly limited, and examples thereof include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, p, A p′-diphenylene ether group, a p, p′-diphenylenecarbonyl group, a naphthalene group and the like can be mentioned. The polyarylene sulfide-based resin A may be a homopolymer using the same repeating unit among the repeating units represented by the general formula (I) or a copolymer containing different types of repeating units depending on applications. .

The homopolymer preferably has a p-phenylene sulfide group having a p-phenylene group as an arylene group and a repeating unit. This is because a homopolymer having a p-phenylene sulfide group as a repeating unit has extremely high heat resistance, and exhibits high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded product having very excellent physical properties can be obtained.

As the copolymer, a combination of two or more kinds of arylene sulfide groups different from the arylene sulfide groups containing the above 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 obtaining a molded product having high physical properties such as heat resistance, moldability, and mechanical properties. A polymer containing 70 mol% or more of p-phenylene sulfide groups is more preferred, and a polymer containing 80 mol% or more is more preferred. The polyarylene sulfide-based resin A having a phenylene sulfide group is a polyphenylene sulfide resin (PPS resin).

The polyarylene sulfide-based resin A is generally known to have a molecular structure that is substantially linear and has no branching or cross-linking structure, and one that has a branching or cross-linking structure depending on the production method. In the form, any type is effective.

The melt viscosity of the polyarylene sulfide-based resin A measured at 310 ° C. and a shear rate of 1216 sec ⁻¹ is preferably 5 Pa · s or more and 50 Pa · s or less, and is 7 Pa · s or more and 40 Pa · s or less. It is more preferable. When the melt viscosity is 5 Pa · s or more and 50 Pa · s or less, excellent high and low temperature impact properties and good fluidity can be maintained.

The production method of the polyarylene sulfide-based resin A is not particularly limited, and can be produced by a conventionally known production method. For example, the polyarylene sulfide-based resin A can be produced by synthesizing a low-molecular-weight polyarylene sulfide-based resin A and then polymerizing it at a high temperature in the presence of a known polymerization aid to increase the molecular weight.

(Fibrous inorganic filler B1)
“Fibrous” refers to a shape having a different diameter ratio of 1 or more and 10 or less and an aspect ratio of more than 2 and 1500 or less. “Flat shape” (a different diameter ratio is larger than 10 and the aspect ratio is later described) 1 to 1500 or less) and “granular” (different diameter ratio of 1 to 10 and aspect ratio of 1 to 2). The “different diameter ratio” is the ratio of the major axis to the minor axis of the section perpendicular to the longitudinal direction. Specifically, the “major axis of the section perpendicular to the longitudinal direction (longest linear distance of the section) / minor axis ( The longest straight distance in the direction perpendicular to the major axis) ”. The “aspect ratio” is “the longest linear distance in the longitudinal direction / the short diameter of the cross section perpendicular to the longitudinal direction (the“ longest linear distance in the cross section ”and the longest linear distance in the perpendicular direction)”. These shapes are all initial shapes (shapes before melt kneading). Both the different diameter ratio and the aspect ratio can be calculated using a scanning electron microscope and image processing software.

In the present embodiment, the fibrous inorganic filler B1 has a different diameter ratio of 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more. The upper limit of the different diameter ratio is 10.0 or less, preferably 8.0 or less, and more preferably 6.0 or less. By containing the fibrous inorganic filler B1 having such a different diameter ratio, the anisotropy of the molding shrinkage rate and the linear expansion coefficient of the insert molded product is reduced, and the high-temperature impact property and the mechanical properties are improved. be able to.

The material of the fibrous inorganic filler B1 is glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber. Mineral fiber such as potassium titanate fiber, stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, brass fiber, etc., polyamide fiber, high molecular weight polyethylene fiber, aramid fiber, polyester fiber, fluorine fiber, etc. A synthetic fiber is mentioned, These can be used 1 type or 2 or more types. Among these, glass fiber and carbon fiber are preferable.

Examples of the fibrous inorganic filler B1 include a fibrous inorganic filler whose cross-sectional shape perpendicular to the longitudinal direction is an oval, an ellipse, a semicircle, an eyebrow, a rectangle, or a similar shape thereof. it can. The “eyebrows shape” is a shape in which the vicinity of the center in the longitudinal direction of an oval is recessed inward.

The cross-sectional area of the fibrous inorganic filler B1 is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mm ² in terms of ease of manufacturing and the effect of combination with the non-fibrous inorganic filler B2. Is preferably 1 × 10 ⁻⁴ to 5 × 10 ⁻⁴ mm ² . “Cross-sectional area” is the longest diameter when the longest straight distance of the cross section of the fibrous inorganic filler B1 measured using a scanning electron microscope and image processing software is the longest diameter, and the shortest straight distance is the shortest diameter. A value obtained by multiplying a value obtained by multiplying the minor axis by a circumferential ratio π can be obtained.
The average length of the fibrous inorganic filler B1 is not particularly limited, but the average fiber length in the molded product is preferably 50 to 1000 μm in consideration of the mechanical properties and molding processability of the molded product. The “average fiber length” is a mean value obtained by measuring the length of several tens (for example, 50) fiber pieces using a scanning electron microscope and image processing software. Further, for the purpose of reducing the specific gravity of the resin composition, it is possible to use hollow fibers as the fibrous inorganic filler B1.

The fibrous inorganic filler B1 may be surface-treated with various surface treatment agents such as generally known epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. By the surface treatment, the adhesion with the polyarylene sulfide-based resin A can be improved. The surface treatment agent may be applied to the fibrous inorganic filler B1 in advance before the material preparation and subjected to a surface treatment or a convergence treatment, or may be added simultaneously with the material preparation.

The mass ratio B1 / B2 of the fibrous inorganic filler B1 and the non-fibrous inorganic filler B2 described later is more than 1.0, preferably 1.2 or more and 4.0 or less. When the mass ratio B1 / B2 exceeds 1.0, even when the resin composition is used for an insert molded product having a structure in which the high-temperature impact resistance is likely to be reduced, excellent high-temperature impact resistance and excellent low warpage Can be achieved at the same time.

The content of the fibrous inorganic filler B1 is preferably 20 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide-based resin A, and the effect of the combination with the non-fibrous inorganic filler B2 is further enhanced. It is more preferably 30 parts by mass or more, more preferably 35 parts by mass with respect to 100 parts by mass of the polyarylene sulfide-based resin A, in that the impact property can be further improved and further low warpage can be achieved at the same time. Part or more and 80 parts by weight or less.

(Non-fibrous inorganic filler B2)
Examples of the non-fibrous inorganic filler B2 include a granular inorganic filler and a plate-like inorganic filler. Powdered inorganic fillers include carbon black, silica, quartz powder, glass beads, glass powder, talc (granular), silicates such as calcium silicate, aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide Metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, various metal powders and the like. Examples of the plate-like inorganic filler include glass flakes, talc (plate-like), mica, kaolin, clay, alumina, and various metal foils.

Among these, it is preferable to contain one or more selected from powdered inorganic fillers, and it is more preferable to contain calcium carbonate or glass beads. The content of the particulate inorganic filler is preferably 50% by mass or more, or 90% by mass or more in the non-fibrous inorganic filler B2. By making content of a granular inorganic filler into the said range, the improvement effect of the high and low temperature impact property by the combination of fibrous inorganic filler B1 and non-fibrous inorganic filler B2 can be heightened more. The non-fibrous inorganic filler B2 may be configured to be calcium carbonate and / or glass beads.

The average particle size (50% d) of the non-fibrous inorganic filler B2 is that the mechanical strength and high-temperature impact resistance are further improved, and the granular filler is in the initial shape (the shape before melt-kneading). It is preferably 10 μm or more, more preferably 12 μm or more, and further preferably 15 μm or more. The upper limit is preferably 50 μm or less, more preferably 45 μm or less, and more preferably 40 μm or less. The plate-like filler is preferably 10 μm or more and 1000 μm or less, more preferably 15 μm or more and 900 μm or less, and particularly preferably 20 μm or more and 800 μm or less in the initial shape (the shape before melt-kneading). preferable. The average particle diameter (50% d) means a median diameter of 50% integrated value in the particle size distribution measured by the laser diffraction / scattering method.

The content of the non-fibrous inorganic filler B2 is preferably 10 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide-based resin A, and the polyarylene is further improved in terms of mechanical strength and high-temperature impact resistance. The amount is more preferably 20 parts by mass or more with respect to 100 parts by mass of the sulfide-based resin A. The upper limit of the blending amount of the non-fibrous inorganic filler B2 is preferably set to 60 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A in terms of suppressing reduction in mechanical properties. Preferably it is 55 mass parts or less.

The total content of the fibrous inorganic filler B1 and the non-fibrous inorganic filler B2 is preferably 40 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide resin A, and the characteristics of the polyarylene sulfide-based resin A are maintained. However, it is more preferably 70 parts by weight or more and 220 parts by weight or less, and more preferably 80 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin A in terms of exerting the action by the combination of the inorganic fillers B1 and B2. Part to 200 parts by weight.

(Fibrous inorganic filler B3)
In the resin composition, the content of the fibrous inorganic filler B3 having a different diameter ratio of 2.0 or less is 50 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A. The content of the fibrous inorganic filler B3 can be 30 parts by mass or less, or less than 10 parts by mass. By suppressing the content of the fibrous inorganic filler B3 to 50 parts by mass or less, the anisotropy of the molding shrinkage rate and the linear expansion coefficient of the insert molded product can be further reduced, and as a result, the high and low temperature impact properties can be further increased. Can be increased. The content of the fibrous inorganic filler B3 is preferably as small as possible, and more preferably not substantially contained. “Substantially free” means a content that does not significantly affect the physical properties of the resin composition. For example, the content of the fibrous inorganic filler B3 in the resin composition is 5% by mass or less. More preferably, it is 4 mass% or less. Examples of the fibrous inorganic filler B3 include a general fibrous inorganic filler whose cross-sectional shape perpendicular to the longitudinal direction is circular or substantially circular. As a material of fibrous inorganic filler B3, the thing similar to the material of above-described fibrous inorganic filler B1 can be mentioned, for example.

(Olefin copolymer C)
The olefin copolymer C contains a structural unit derived from α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid as a copolymerization component. Since such an olefin copolymer C is contained, the high and low temperature impact property of an insert molded product can be remarkably improved. The olefin copolymer C is preferably an olefin copolymer containing a structural unit derived from a (meth) acrylic acid ester. The olefin copolymer can be used alone or in combination of two or more. 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 the like. Of these, ethylene is preferable. As the α-olefin, one or more selected from the above can be used. The content of the copolymer component derived from the α-olefin is not particularly limited, but can be, for example, 1% by mass or more and 8% by mass or less in the total resin composition.

Examples of the glycidyl ester of α, β-unsaturated acid include those having a structure represented by the following general formula (II).

(However, R1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.)

Examples of the compound represented by the general formula (II) include glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl ethacrylate, and the like. Of these, glycidyl methacrylate is preferable. The glycidyl ester of α, β-unsaturated acid can be used alone or in combination of two or more. The content of the copolymer component derived from the glycidyl ester of α, β-unsaturated acid is preferably 0.05% by mass or more and 0.6% by mass or less in the total resin composition. When the content of the copolymer component derived from the glycidyl ester of α, β-unsaturated acid is within this range, the deposition of mold deposits can be further suppressed while maintaining high and low temperature impact properties.

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 Acid-n-octyl, methacrylic acid ester (eg, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, isopropyl methacrylate, methacrylate-n-butyl, methacrylate isobutyl, methacrylate-n-amyl, methacrylate) Acid-n-octyl) and the like. Of these, methyl acrylate is preferred. The (meth) acrylic acid ester can be used alone or in combination of two or more. Although content of the copolymerization component derived from (meth) acrylic acid ester is not specifically limited, For example, it can be 0.5 mass% or more and 3 mass% or less in all the resin compositions.

Olefin-based copolymer containing a structural unit derived from α-olefin and a structural unit derived from a glycidyl ester of α, β-unsaturated acid, and an olefin-based copolymer containing a structural unit derived from (meth) acrylic acid ester The coalescence can be produced by performing copolymerization by a conventionally known method. For example, the olefin copolymer can be obtained by copolymerization by a well-known radical polymerization reaction. The type of the olefin copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Examples of the olefin copolymer include polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, 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.

The olefin copolymer used in the present embodiment can contain structural units derived from other copolymer components as long as the effects of the present invention are not impaired.

More specifically, examples of the olefin copolymer include a glycidyl methacrylate-modified ethylene copolymer and a glycidyl ether-modified ethylene copolymer. Among them, a glycidyl methacrylate-modified ethylene copolymer is preferable.

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” (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 olefin copolymer C may be 3 parts by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide-based resin A in terms of suppressing mold deposit while further improving high and low temperature impact properties. Preferably, it can be 5 parts by mass or more and 30 parts by mass or less, 7 parts by mass or more and 25 parts by mass or less, or 7 parts by mass or more and 20 parts by mass or less.

(Other additives)
The resin composition is a known additive that is generally added to a thermoplastic resin and a thermosetting resin in order to impart desired characteristics according to the purpose within a range not impairing the effects of the present invention, that is, burr suppression. Agents, mold release agents, lubricants, plasticizers, flame retardants, coloring agents such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, thermal stabilizers, weathering stabilizers, corrosion inhibitors, etc. Can be blended according to the required performance. Examples of the burr suppressor include branched polyphenylene sulfide resins and silane compounds having a very high melt viscosity as described in International Publication No. 2006/068161 and International Publication No. 2006/068159. be able to. Examples of the silane compound include various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, and mercapto silane. For example, vinyl trichlorosilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Examples include γ-aminopropyltriethoxysilane and γ-mercaptotrimethoxysilane, but are not limited thereto. The content of the additive can be, for example, 5% by mass or less in the total resin composition.

In addition to the above-mentioned components, other thermoplastic resin components can be supplementarily used in a small amount in combination with the resin composition depending on the purpose. Any other thermoplastic resin may be used as long as it is stable at high temperatures. For example, aromatic polyester such as polyethylene terephthalate, polybutylene terephthalate, aromatic dicarboxylic acid and diol, or oxycarboxylic acid, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfone, polyethersulfone, poly Examples include ether imide, polyether ketone, and fluororesin. Moreover, these thermoplastic resins can also be used in mixture of 2 or more types. The content of other thermoplastic resin components can be, for example, 20% by mass or less, 15% by mass or less, or 10% by mass or less in the total resin composition.

The resin composition can be easily prepared using equipment and methods generally used as a conventional resin composition preparation method. For example, 1) A method in which each component is mixed and then kneaded and extruded by a single-screw or twin-screw extruder to prepare pellets, and thereafter molded, 2) once pellets having different compositions are prepared, and a predetermined amount of the pellets are prepared Any of a method of mixing and molding to obtain a molded product of the desired composition after molding, 3) a method of directly charging one or more of each component into a molding machine, etc. can be used. Further, a method of adding a part of the resin component as a fine powder and mixing it with other components is a preferable method for achieving uniform blending of these components.

[Insert molded product]
The insert molded product includes an insert member formed using a metal, an alloy, or an inorganic solid material, and a resin member that covers at least a part of the surface of the insert member. The resin member is formed using the polyarylene sulfide-based resin composition, and includes the resin composition. Since a resin member contains the said resin composition, it can be set as the insert molded product excellent in high-low temperature impact property.

The metal, alloy, or inorganic solid material constituting the insert member is not particularly limited, but is preferably one that does not deform or melt when it comes into contact with the resin composition during molding. Examples thereof include metals such as aluminum, magnesium, copper, and iron, alloys of the above metals such as brass, and inorganic solids such as glass and ceramics.

The shape and size of the insert molded product are not particularly limited, and can be a shape according to the application. In particular, a resin member containing the above-described resin composition can achieve excellent high and low temperature impact properties even when it has a structure in which high and low temperature impact properties are likely to decrease. Therefore, the insert molded product has either or both of a weld part and a stress concentration part, and the thickness of at least a part of the weld part and / or the stress concentration part is 2 mm or less, or 1.5 mm or less. You may have a structure.

Furthermore, the insert-molded product may have a structure in which the resin member has both a weld portion and a stress concentration portion, and both are coincident at least in a part of the region. For example, the insert molded product 1 shown in FIG. 1 has an insert member 11 and a resin member 10 that covers at least a part of the insert member 11 over the entire circumference. The insert member 11 has a corner portion formed by two side surfaces, and a stress concentration portion is formed from the ridge line of the corner portion to the side surface of the resin member 10. In this insert-molded product 11, when a trace of the resin injection port (gate trace) is formed on the side surface of the resin member 10 on the side opposite to the region in contact with the corner of the insert member 11, The weld portion which is a joint portion is formed in a region which coincides with the stress concentration portion in at least a part of the region. The insert molded product 11 obtained in this case has a structure in which the weld portion and the stress concentration portion coincide at least in a part of the region.

In addition, the “weld part” is a part where the flow ends of the resin composition are joined (welded) to each other, and generally has a tendency to have lower mechanical strength than other parts. Therefore, the weld portion tends to be inferior in high and low temperature impact than other portions. The “stress concentration part” is a part where stress generated by expansion and contraction of the resin composition is concentrated. For example, a corner part (corner part), a notch part, a scratch part, a through hole, a thinned part, a thin part, Examples include a portion having a large change in thickness and a flow mark portion. Therefore, when the resin member has both the weld portion and the stress concentration portion, and the above-described structure in which both are coincident in at least a part of the region, the high-temperature impact resistance is usually significantly inferior. However, when the insert molded product according to the present embodiment has such a structure, the effect of increasing the high and low temperature impact property is more remarkably exhibited.

The insert molded product has a shape in which the ratio t ₁ / t ₂ between the thickness t ₁ of the region of the resin member on the side where the resin injection hole is traced and the thickness t ₂ of the thinnest region is 3 or more. You may have. Further, in the insert molded product, the insert member may have a corner portion (corner portion), and the curvature radius r of the tip portion of the corner portion may be 0.8 mm or less, or 0.5 mm or less.

The method for producing the insert-molded product is not particularly limited, and for example, the above-described resin composition and an insert member that has been previously molded into a desired shape can be insert-molded. In insert molding, for example, an insert member is mounted in advance on a mold, and the resin composition is filled on the outside by injection molding, extrusion compression molding, or the like, and then composite molding can be performed.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the interpretation of the present invention is not limited by these examples.

[Examples 1 to 9, Comparative Examples 1 to 4]
Using the materials shown below, a polyarylene sulfide-based resin, a fibrous inorganic filler, a non-fibrous inorganic filler, and an olefin copolymer were dry blended in the compositions and content ratios shown in Tables 1 and 2. This was put into a twin screw extruder having a cylinder temperature of 320 ° C. and melt kneaded to obtain resin composition pellets of Examples and Comparative Examples.

(Polyarylene sulfide resin)
Polyarylene sulfide-based resin A: Polyphenylene sulfide resin (PPS), “Fortron KPS” manufactured by Kureha Corporation (melt viscosity: 20 Pa · s (shear rate: 1216 sec ⁻¹ , 310 ° C.))

(Measurement of melt viscosity of polyarylene sulfide resin)
The melt viscosity of the polyarylene sulfide-based resin A was measured as follows.
Using a Capillograph manufactured by Toyo Seiki Seisakusho, using a 1 mmφ × 20 mmL / flat die as a capillary, the melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1216 sec ⁻¹ was measured.

(Inorganic filler)
Fibrous inorganic filler B1: Glass fiber, oval cross section, major axis 28 μm, minor axis 7 μm, major axis / minor axis ratio 4.0, “Non-shaped cross-section chopped strand CSG 3PA-830” manufactured by Nitto Boseki Co., Ltd.
Non-fibrous inorganic filler B2: Calcium carbonate, average particle size (50% d) 25 μm, “MC-35W” manufactured by Asahi Mizue Co., Ltd.
Non-fibrous inorganic filler B2: Glass beads, average particle size (50% d) 20 μm, “EGB731A” manufactured by Potters Barotini Co., Ltd.
Non-fibrous inorganic filler B2: glass flake, average particle size (50% d) 600 μm, “REFG-108” manufactured by Nippon Sheet Glass Co., Ltd.
Fibrous inorganic filler B3: Glass fiber, cross-sectionally eyebrows, major axis 24 μm, minor axis 12 μm, major axis / minor axis ratio 2.0, “Non-shaped cross-section chopped strand CSH 3PA-860”

(Olefin copolymer)
Olefin-based copolymer C: “Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd. As a copolymer component, 67% by mass of ethylene, 6% by mass of glycidyl methacrylate, and 27% by mass of methyl acrylate are included.

[Evaluation]
(High and low temperature impact)
Using the resin composition and a metal insert member, the test pieces shown in FIGS. 1 to 3 were insert-molded by injection molding to evaluate high and low temperature impact properties. FIG. 1 is a diagram showing an insert-molded test piece 1, FIG. 2 is a diagram showing an insert member 11, and FIG. 3 is a diagram showing dimensions of the test piece 1. As shown in FIG. 1, the test piece 1 is molded in a state in which a metal insert member 11 is embedded in a cylindrical resin member 10 made of a resin composition. The cylindrical resin member 10 is formed using the pellets obtained as described above. As shown in FIG. 2, the insert member 11 has a columnar shape, and the shape of the upper surface and the bottom surface of the insert member 11 is a teardrop shape having an arc shape on one side and an acute angle on the other side. As shown in FIG. 2B, which is a partially enlarged view, the acute-angle shaped portion has an arcuate tip, and the radius of curvature r is 0.2 mm. Moreover, the insert member 11 is higher than the height of the columnar resin member 10, and a part thereof protrudes (see FIG. 1A). Further, as shown in FIG. 3A, the center O _{1 of} the circle partially including the arc of the insert member 11 does not coincide with the center O ₂ of the circle of the resin member 10, and the acute angle shape of the insert member 11 It arrange | positions so that the side may adjoin to the side surface of the resin member 10. FIG. The distance dw between the acute-angled tip of the insert member 11 and the side surface of the resin member 10 is 1 mm. In the resin member 10, the vicinity of the acute-angled tip of the insert member 11 forms a stress concentration portion. And it is the thinnest region. In addition, although the numerical value is shown about the dimension of the test piece in FIG. 3, the unit is mm. In the test piece 1, the trace of the resin injection port (gate trace) is formed on the side surface opposite to the side surface closest to the acute-angle shape of the insert member 11. In this case, the weld portion is formed on the side surface closest to the acute angle shape of the insert member 11.

Using the thermal shock tester (manufactured by Espec Co., Ltd.) for the above test piece, the cycle of cooling at −40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours is repeated every 20 cycles. The weld was observed. The number of cycles when a crack occurred in the weld was evaluated as an index of high and low temperature impact properties. The results are shown in Tables 1 and 2. When the number of cycles is 230 or more, the high / low temperature impact resistance is excellent, and when it is 260 or more, the high / low temperature impact resistance is particularly excellent.

(Low warpage)
Using the resin compositions obtained in the examples and comparative examples, a flat resin of 80 mm × 80 mm × 1.5 mm in thickness is obtained by injection molding under the conditions of a cylinder temperature of 320 ° C., a mold temperature of 150 ° C., and a holding pressure of 70 MPa. Five molded products 2 were produced. The first flat plate-shaped resin molded product 2 is placed on a horizontal plane, and a CNC image measuring machine (model: QVBHU404-PRO1F) manufactured by Mitutoyo Corporation is used at nine locations on the flat plate-shaped resin molded product 2. The height from the horizontal plane was measured, and the average height was calculated from the obtained measurement values. FIG. 4 shows the positions where the heights are measured with black circles (d ₁ = 3 mm, d ₂ = 37 mm). The height from the horizontal plane was the same as the average height, and a plane parallel to the horizontal plane was used as a reference plane. The maximum height and the minimum height from the reference plane were selected from the heights measured at the nine locations, and the difference between them was calculated. Similarly, for the other four flat resin molded products, the above difference was calculated, and the obtained five values were averaged to obtain the value of warpage. The results are shown in Tables 1 and 2. The smaller the amount of warpage, the better the low warpage.

DESCRIPTION OF SYMBOLS 1 Test piece 2 Flat resin molded product 10 Resin member 11 Insert member 100 Molded product

Claims

Polyarylene sulfide-based resin A, fibrous inorganic filler B1, non-fibrous inorganic filler B2, and a non-fibrous inorganic filler B2 having a different diameter ratio of 3.0 or more, which is a ratio of a major axis to a minor axis of a cross section perpendicular to the longitudinal direction, and α An olefin copolymer C containing a structural unit derived from an olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid,
The mass ratio B1 / B2 of the fibrous inorganic filler B1 and the non-fibrous inorganic filler B2 exceeds 1.0,
The content of the fibrous inorganic filler B3 having a different diameter ratio of 2.0 or less, which is the ratio of the major axis to the minor axis in the cross section perpendicular to the longitudinal direction, is 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide-based resin A. A polyarylene sulfide-based resin composition which is the following.
The polyarylene sulfide-based resin composition according to claim 1, wherein the content of the fibrous inorganic filler B1 is 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A.
The polyarylene sulfide-based resin composition according to claim 1 or 2, wherein the content of the non-fibrous inorganic filler B2 is 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide-based resin A.
The polyarylene sulfide-based resin composition according to any one of claims 1 to 3, wherein the non-fibrous inorganic filler B2 has an average particle size of 10 µm or more.
The polyarylene sulfide-based resin composition according to any one of claims 1 to 4, wherein the non-fibrous inorganic filler B2 includes a granular inorganic filler.
The polyarylene sulfide-based resin composition according to any one of claims 1 to 5, wherein the non-fibrous inorganic filler B2 contains one or both of calcium carbonate and glass beads.
The polyarylene sulfide system according to any one of claims 1 to 6, wherein the content of the olefin copolymer C is 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin A. Resin composition.
The polyarylene sulfide-based resin composition according to any one of claims 1 to 7, which is substantially free of fibrous inorganic filler B3.
It has an insert member formed using a metal, an alloy, or an inorganic solid substance, and a resin member which covers at least a part of the surface of the insert member, The resin member according to any one of claims 1 to 8. An insert-molded article formed using the polyarylene sulfide-based resin composition described above.
The resin member has either or both of a weld part where flow ends of the resin composition are joined and a stress concentration part where stress generated by expansion and contraction concentrates, and the weld part and / or the stress concentration. The insert molded product according to claim 9, wherein the thickness of at least a part of the region is 2 mm or less.