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

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

Info

Publication number
WO2018198850A1
WO2018198850A1 PCT/JP2018/015670 JP2018015670W WO2018198850A1 WO 2018198850 A1 WO2018198850 A1 WO 2018198850A1 JP 2018015670 W JP2018015670 W JP 2018015670W WO 2018198850 A1 WO2018198850 A1 WO 2018198850A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic filler
mass
fibrous inorganic
polyarylene sulfide
resin composition
Prior art date
Application number
PCT/JP2018/015670
Other languages
French (fr)
Japanese (ja)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Publication of WO2018198850A1 publication Critical patent/WO2018198850A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • 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.
  • 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.
  • the high and low temperature impact resistance may be reduced.
  • Patent Document 1 there is a technique of blending a polyarylene sulfide-based resin with a fibrous filler having a flat cross-sectional shape
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the average particle diameter of the non-fibrous inorganic filler B2 is preferably 10 ⁇ m 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • fibrous inorganic filler B1 examples 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 ⁇ 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 ⁇ m 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.
  • 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 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.
  • the plate-like inorganic filler include glass flakes, talc (plate-like), mica, kaolin, clay, alumina, and various metal foils.
  • 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.
  • 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 ⁇ m or more, more preferably 12 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the upper limit is preferably 50 ⁇ m or less, more preferably 45 ⁇ m or less, and more preferably 40 ⁇ m or less.
  • the plate-like filler is preferably 10 ⁇ m or more and 1000 ⁇ m or less, more preferably 15 ⁇ m or more and 900 ⁇ m or less, and particularly preferably 20 ⁇ m or more and 800 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the olefin copolymer C contains a structural unit derived from ⁇ -olefin and a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -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.
  • (meth) acrylic acid ester is also referred to as (meth) acrylate.
  • glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid
  • (meth) acrylate” means both acrylate and methacrylate.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene and the like. Of these, ethylene is preferable. As the ⁇ -olefin, one or more selected from the above can be used.
  • the content of the copolymer component derived from the ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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.
  • methyl acrylate is preferred.
  • the (meth) acrylic acid ester can be used alone or in combination of two or more.
  • 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 ⁇ -olefin and a structural unit derived from a glycidyl ester of ⁇ , ⁇ -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.
  • 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.
  • olefin copolymer examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the silane compound examples include various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, and mercapto silane.
  • vinyl trichlorosilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane examples include ⁇ -aminopropyltriethoxysilane and ⁇ -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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the 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.
  • 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.
  • 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.
  • 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.
  • 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 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.))
  • 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 mm ⁇ ⁇ 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.
  • Fibrous inorganic filler B1 Glass fiber, oval cross section, major axis 28 ⁇ m, minor axis 7 ⁇ m, 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 ⁇ m, “MC-35W” manufactured by Asahi Mizue Co., Ltd.
  • Non-fibrous inorganic filler B2 Glass beads, average particle size (50% d) 20 ⁇ m, “EGB731A” manufactured by Potters Barotini Co., Ltd.
  • Non-fibrous inorganic filler B2 glass flake, average particle size (50% d) 600 ⁇ m, “REFG-108” manufactured by Nippon Sheet Glass Co., Ltd.
  • Fibrous inorganic filler B3 Glass fiber, cross-sectionally eyebrows, major axis 24 ⁇ m, minor axis 12 ⁇ m, major axis / minor axis ratio 2.0, “Non-shaped cross-section chopped strand CSH 3PA-860”
  • Olefin-based copolymer C “Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd.
  • a copolymer component 67% by mass of ethylene, 6% by mass of glycidyl methacrylate, and 27% by mass of methyl acrylate are included.
  • FIG. 1 is a diagram showing an insert-molded test piece 1
  • FIG. 2 is a diagram showing an insert member 11
  • FIG. 3 is a diagram showing dimensions of the test piece 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.
  • 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.
  • the acute-angle shaped portion has an arcuate tip, and the radius of curvature r is 0.2 mm.
  • 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.
  • 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
  • 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.
  • the vicinity of the acute-angled tip of the insert member 11 forms a stress concentration portion. And it is the thinnest region.
  • the numerical value is shown about the dimension of the test piece in FIG. 3, the unit is mm.
  • 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.
  • the weld portion is formed on the side surface closest to the acute angle shape of the insert member 11.
  • 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.
  • a CNC image measuring machine model: QVBHU404-PRO1F

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

ポリアリーレンサルファイド系樹脂組成物及びインサート成形品Polyarylene sulfide-based resin composition and insert molded product
　本発明は、ポリアリーレンサルファイド系樹脂組成物及びインサート成形品に関する。 The present invention relates to a polyarylene sulfide-based resin composition and an insert molded product.
　インサート成形品は、金属や無機固体物等からなるインサート部材と熱可塑性樹脂組成物からなる樹脂部材とを一体的に成形した成形品であり、自動車部品や電気電子部品、ＯＡ機器部品等の広い分野に応用されている。しかし、インサート成形品を構成する金属等と熱可塑性樹脂組成物とは、温度変化による熱膨張率や収縮率が大きく異なるため、使用中の温度変化でインサート成形品が破壊してしまう場合がある。そのため、インサート成形品には、高低温衝撃性（耐ヒートショック性）が求められている。 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.
　ポリアリーレンサルファイド系樹脂は、熱可塑性樹脂の中では比較的に高低温衝撃性が優れている樹脂として知られている。しかし、ポリアリーレンサルファイド系樹脂は、靱性に乏しく脆弱であるため、例えばハイブリットカーに用いられるパワーモジュールやリアクトル等の部品のように、インサート部材の構造が複雑でありかつ樹脂部材が肉厚変化の大きい部分を有する場合や、自動車のエンジン回りの部品のように、使用される環境の高低温度変化が大きい場合は、高低温衝撃性が低下してしまう場合がある。これらの問題を解決する方法として、ポリアリーレンサルファイド系樹脂に扁平な断面形状を有する繊維状の充填剤を配合する技術がある（特許文献１）。 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).
　また、ポリアリーレンサルファイド系樹脂は、結晶性樹脂であるため、冷却過程における樹脂の収縮率が樹脂の流動方向とその直角方向とで異なる、いわゆる収縮率の異方性を有している。こうした収縮率の異方性によって、得られるインサート成形品に反りやひけが生じて寸法精度が低下する場合がある。ひけの発生を抑制する方法として、特定のＮａ含有量で、かつレジンのｐＨが特定の範囲である実質的に直鎖状のポリアリーレンサルファイド樹脂に、扁平な断面形状を有する繊維状強化剤を配合する技術がある（特許文献２）。
特開２００５－１６１６９３号公報 特開２００６－３２８２９１号公報 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
　本発明は、高低温衝撃性及び低反り性が優れるポリアリーレンサルファイド系樹脂組成物及びその樹脂組成物を用いたインサート成形品を提供することを課題とする。 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.
　本発明者は研究の過程で、ポリアリーレンサルファイド系樹脂に配合する無機充填剤として、所定の異径比を有する繊維状無機充填剤と非繊維状無機充填剤とを所定の割合で組み合わせて配合することによって、樹脂組成物を高低温衝撃性が低下しやすい構造を有するインサート成形品の樹脂部材に用いた場合でも、より優れた高低温衝撃性を達成できることを見出し、本発明を完成するに至った。 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.
　すなわち、本発明に係るポリアリーレンサルファイド系樹脂組成物は、ポリアリーレンサルファイド系樹脂Ａ、長手方向に直角な断面の長径と短径との比である異径比が３．０以上である繊維状無機充填剤Ｂ１、非繊維状無機充填剤Ｂ２、及びα－オレフィン由来の構成単位とα，β－不飽和酸のグリシジルエステル由来の構成単位とを含有するオレフィン系共重合体Ｃを含有し、繊維状無機充填剤Ｂ１及び非繊維状無機充填剤Ｂ２の質量比Ｂ１／Ｂ２が１．０を超え、長手方向に直角な断面の長径と短径との比である異径比が２．０以下である繊維状無機充填剤Ｂ３の含有量がポリアリーレンサルファイド系樹脂Ａ１００質量部に対して５０質量部以下である。 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.
　本発明において、繊維状無機充填剤Ｂ１の含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３０質量部以上８０質量部以下であることが好ましい。また、非繊維状無機充填剤Ｂ２の含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して２０質量部以上６０質量部以下であることが好ましい。 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.
　本発明において、非繊維状無機充填剤Ｂ２の平均粒子径が１０μｍ以上であることが好ましい。また、非繊維状無機充填剤Ｂ２が粉粒状無機充填剤を含むことが好ましい。粉粒状無機充填剤は、炭酸カルシウム及びガラスビーズのいずれか又は両方を含むことが好ましい。 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.
　本発明において、オレフィン系共重合体Ｃの含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３質量部以上３０質量部以下であることが好ましい。５質量部以上３０質量部以下であることがより好ましい。 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.
　本発明において、繊維状無機充填剤Ｂ３を実質的に含まないことが好ましい。 In the present invention, it is preferable that the fibrous inorganic filler B3 is not substantially contained.
　本発明に係るインサート成形品は、金属、合金又は無機固体物を用いて形成されたインサート部材と、インサート部材の表面の少なくとも一部を覆う樹脂部材とを有し、樹脂部材が上記ポリアリーレンサルファイド系樹脂組成物を用いて形成されたことを特徴とする。 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.
　本発明において、樹脂部材が、前記樹脂組成物の流動末端同士が接合したウェルド部、及び膨張収縮により発生する応力が集中する応力集中部のいずれか又は両方を有し、ウェルド部及び／又は応力集中部の少なくとも一部の領域の厚さが２ｍｍ以下であるように構成することができる。 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.
　本発明によれば、高低温衝撃性及び低反り性が優れるポリアリーレンサルファイド系樹脂組成物及びその樹脂組成物を用いたインサート成形品を提供することができる。 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.
高低温衝撃性試験で用いた試験片（インサート成形品）を模式的に示す図であって、（ａ）は斜視図であり、（ｂ）は平面図である。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. 図１に示すインサート成形品のインサート部材を示す図であって、（ａ）は斜視図であり、（ｂ）は鋭角形状部分の拡大平面図である。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. 図１に示す試験片の寸法（ｍｍ）についての説明図であって、（ａ）は平面図、（ｂ）は側面図である。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. 低反り性の測定位置についての説明図である。It is explanatory drawing about the measurement position of low curvature property.
　以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。 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.
［ポリアリーレンサルファイド系樹脂組成物］
　ポリアリーレンサルファイド系樹脂組成物（以下、単に「樹脂組成物」ともいう。）は、ポリアリーレンサルファイド系樹脂を主成分とする樹脂を含む樹脂組成物である。「主成分とする」とは、樹脂成分中、８０質量％以上、８５質量％以上、９０質量％以上であることを意味する。本実施形態に係る樹脂組成物は、ポリアリーレンサルファイド系樹脂Ａ、異径比が３．０以上である繊維状無機充填剤Ｂ１、非繊維状無機充填剤Ｂ２、及びオレフィン系共重合体Ｃを含有する。 [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.
（ポリアリーレンサルファイド系樹脂Ａ）
　ポリアリーレンサルファイド系樹脂Ａは、以下の一般式（Ｉ）で示される繰り返し単位を有する樹脂である。
　－（Ａｒ－Ｓ）－　　・・・（Ｉ）
　（但し、Ａｒは、アリーレン基を示す。） (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.)
　アリーレン基は、特に限定されないが、例えば、ｐ－フェニレン基、ｍ－フェニレン基、ｏ－フェニレン基、置換フェニレン基、ｐ，ｐ’－ジフェニレンスルフォン基、ｐ，ｐ’－ビフェニレン基、ｐ，ｐ’－ジフェニレンエーテル基、ｐ，ｐ’－ジフェニレンカルボニル基、ナフタレン基等を挙げることができる。ポリアリーレンサルファイド系樹脂Ａは、上記一般式（Ｉ）で示される繰り返し単位の中で、同一の繰り返し単位を用いたホモポリマーの他、用途によっては異種の繰り返し単位を含むコポリマーとすることができる。 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. .
　ホモポリマーとしては、アリーレン基としてｐ－フェニレン基を有する、ｐ－フェニレンサルファイド基を繰り返し単位とするものが好ましい。ｐ－フェニレンサルファイド基を繰り返し単位とするホモポリマーは、極めて高い耐熱性を持ち、広範な温度領域で高強度、高剛性、さらに高い寸法安定性を示すからである。このようなホモポリマーを用いることで非常に優れた物性を備える成形品を得ることができる。 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.
　コポリマーとしては、上記のアリーレン基を含むアリーレンサルファイド基の中で異なる２種以上のアリーレンサルファイド基の組み合わせが使用できる。これらの中では、ｐ－フェニレンサルファイド基とｍ－フェニレンサルファイド基とを含む組み合わせが、耐熱性、成形性、機械的特性等の高い物性を備える成形品を得るという観点から好ましい。ｐ－フェニレンサルファイド基を７０ｍｏｌ％以上含むポリマーがより好ましく、８０ｍｏｌ％以上含むポリマーがさらに好ましい。なお、フェニレンサルファイド基を有するポリアリーレンサルファイド系樹脂Ａは、ポリフェニレンサルファイド樹脂（ＰＰＳ樹脂）である。 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).
　ポリアリーレンサルファイド系樹脂Ａは、一般にその製造方法により、実質的に線状で分岐や架橋構造を有しない分子構造のものと、分岐や架橋を有する構造のものが知られているが、本実施形態においてはその何れのタイプのものについても有効である。 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.
　ポリアリーレンサルファイド系樹脂Ａの溶融粘度は、３１０℃及びせん断速度１２１６ｓｅｃ－１で測定した溶融粘度が、５Ｐａ・ｓ以上５０Ｐａ・ｓ以下であることが好ましく、７Ｐａ・ｓ以上４０Ｐａ・ｓ以下であることがより好ましい。溶融粘度が５Ｐａ・ｓ以上５０Ｐａ・ｓ以下の場合、優れた高低温衝撃性及び良好な流動性を維持することができる。 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.
　ポリアリーレンサルファイド系樹脂Ａの製造方法は、特に限定されず、従来公知の製造方法によって製造することができる。例えば、低分子量のポリアリーレンサルファイド系樹脂Ａを合成後、公知の重合助剤の存在下で、高温下で重合して高分子量化することでポリアリーレンサルファイド系樹脂Ａを製造することができる。 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.
（繊維状無機充填剤Ｂ１）
　「繊維状」とは、異径比が１以上１０以下、かつ、アスペクト比が２を超え１５００以下の形状をいい、後述する「板状」（異径比が１０より大きく、かつアスペクト比が１以上１５００以下の形状）、「粉粒状」（異径比が１以上１０以下、かつ、アスペクト比が１以上２以下）とは区別される。なお、「異径比」とは、長手方向に直角な断面の長径と短径との比であり、詳しくは「長手方向に直角の断面の長径（断面の最長の直線距離）／短径（長径と直角方向の最長の直線距離）」である。「アスペクト比」とは、「長手方向の最長の直線距離／長手方向に直角の断面の短径（「断面の最長の直線距離」と直角方向の最長の直線距離）」である。これらの形状は、いずれも初期形状（溶融混練前の形状）である。異径比及びアスペクト比は、いずれも、走査型電子顕微鏡及び画像処理ソフトを用いて算出することができる。 (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.
　本実施形態では、繊維状無機充填剤Ｂ１は、異径比が３．０以上であり、好ましくは、３．５以上、より好ましくは、３．８以上である。異径比の上限値は、１０．０以下であり、好ましくは、８．０以下であり、より好ましくは、６．０以下である。このような異径比を有する繊維状無機充填剤Ｂ１を含有することで、インサート成形品の成形収縮率及び線膨張係数の異方性を低下させ、高低温衝撃性及び機械的物性を向上させることができる。 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.
　繊維状無機充填剤Ｂ１の材料としては、ガラス繊維、カーボン繊維、酸化亜鉛繊維、酸化チタン繊維、ウォラストナイト、シリカ繊維、シリカ－アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化ケイ素繊維、硼素繊維、チタン酸カリ繊維、等の鉱物繊維、ステンレス繊維、アルミニウム繊維、チタン繊維、銅繊維、真鍮繊維等の金属繊維状物質、ポリアミド繊維、高分子量ポリエチレン繊維、アラミド繊維、ポリエステル繊維、フッ素繊維等の合成繊維が挙げられ、これらを１種又は２種以上用いることができる。中でも、ガラス繊維、カーボン繊維が好ましい。 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.
　繊維状無機充填剤Ｂ１としては、例えば、長手方向に直角な断面形状が、長円形、楕円形、半円、まゆ形、矩形又はこれらの類似形である繊維状の無機充填剤を挙げることができる。なお、「まゆ形」は、長円形の長手方向の中央付近が内側に窪んだ形状である。 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.
　繊維状無機充填剤Ｂ１の断面積は、製造しやすさ及び非繊維状無機充填剤Ｂ２との組み合わせの効果をより高める点で、１×１０－５～１×１０－３ｍｍ２であることが好ましく、１×１０－４～５×１０－４ｍｍ２であることがより好ましい。「断面積」は、走査型電子顕微鏡及び画像処理ソフトを用いて測定した繊維状無機充填剤Ｂ１の断面の最長の直線距離を長径とし、最短の直線距離を短径とした場合に、長径と短径とを乗じた値に更に円周率πを乗じた値とすることができる。
　繊維状無機充填剤Ｂ１の平均長さは、特に限定されないが、成形品の機械的物性、成形加工性等を考慮し、成形品内の平均繊維長で５０～１０００μｍが好ましい。「平均繊維長」は、走査型電子顕微鏡及び画像処理ソフトを用いて、数十本程度（例えば、５０本）の繊維片の長さを測定し、その平均値とする。また、樹脂組成物の比重を軽くする等の目的で、繊維状無機充填剤Ｂ１として中空の繊維を使用することも可能である。 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.
　繊維状無機充填剤Ｂ１は、一般的に知られているエポキシ系化合物、イソシアネート系化合物、シラン系化合物、チタネート系化合物、脂肪酸等の各種表面処理剤により表面処理されていてもよい。表面処理により、ポリアリーレンサルファイド系樹脂Ａとの密着性を向上させることができる。表面処理剤は、材料調製の前に予め繊維状無機充填剤Ｂ１に適用して表面処理又は収束処理を施しておくか、または材料調製の際に同時に添加してもよい。 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.
　繊維状無機充填剤Ｂ１及び後述する非繊維状無機充填剤Ｂ２の質量比Ｂ１／Ｂ２は、１．０を超え、好ましくは１．２以上、４．０以下である。質量比Ｂ１／Ｂ２が１．０を超える場合に、樹脂組成物を高低温衝撃性が低下しやすい構造を有するインサート成形品に用いた場合でも、優れた高低温衝撃性と優れた低反り性を同時に達成することができる。 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.
　繊維状無機充填剤Ｂ１の含有量は、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して２０質量部以上であることが好ましく、非繊維状無機充填剤Ｂ２との組み合わせの効果をより高めて高低温衝撃性をより向上させ、また、さらに低反り性を同時に達成することができる点で、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３０質量部以上であることがより好ましく、さらに好ましくは３５質量部以上、８０質量部以下である。 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.
（非繊維状無機充填剤Ｂ２）
　非繊維状無機充填剤Ｂ２としては、粉粒状無機充填剤、板状無機充填剤等を挙げることができる。粉粒状無機充填剤としては、カーボンブラック、シリカ、石英粉末、ガラスビーズ、ガラス粉、タルク（粒状）、ケイ酸カルシウム、ケイ酸アルミニウム、珪藻土等のケイ酸塩、酸化鉄、酸化チタン、酸化亜鉛、アルミナ等の金属酸化物、炭酸カルシウム、炭酸マグネシウム等の金属炭酸塩、硫酸カルシウム、硫酸バリウム等の金属硫酸塩、その他炭化ケイ素、窒化ケイ素、窒化硼素、各種金属粉末等を挙げることができる。板状無機充填剤としては、例えば、ガラスフレーク、タルク（板状）、マイカ、カオリン、クレイ、アルミナ、各種の金属箔等を挙げることができる。 (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.
　上記のうち、粉粒状無機充填剤から選ばれる１種又は２種以上を含有することが好ましく、炭酸カルシウム又はガラスビーズを含有することがより好ましい。粉粒状無機充填剤の含有量は、非繊維状無機充填剤Ｂ２中に５０質量％以上、又は９０質量％以上とすることが好ましい。粉粒状無機充填剤の含有量を上記範囲にすることで、繊維状無機充填剤Ｂ１及び非繊維状無機充填剤Ｂ２の組み合わせによる高低温衝撃性の向上効果をより高めることができる。非繊維状無機充填剤Ｂ２は、炭酸カルシウム及び／又はガラスビーズであるように構成してもよい。 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.
　非繊維状無機充填剤Ｂ２の平均粒子径（５０％ｄ）は、機械的強度や高低温衝撃性をより向上させる点で、粉粒状充填剤は、初期形状（溶融混練前の形状）において、１０μｍ以上であることが好ましく、１２μｍ以上であることがより好ましく、１５μｍ以上であることがさらに好ましい。また上限値は、５０μｍ以下であることが好ましく、４５μｍ以下であることがより好ましく、４０μｍ以下であることがより好ましい。板状充填剤は、初期形状（溶融混練前の形状）において、１０μｍ以上、１０００μｍ以下であることが好ましく、１５μｍ以上、９００μｍ以下であることがより好ましく、２０μｍ以上、８００μｍ以下であることが特に好ましい。なお、平均粒子径（５０％ｄ）とは、レーザー回折・散乱法により測定した粒度分布における積算値５０％のメジアン径を意味する。 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.
　非繊維状無機充填剤Ｂ２の含有量は、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して１０質量部以上であることが好ましく、機械的強度や高低温衝撃性をより向上させる点で、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して、２０質量部以上であることがより好ましい。非繊維状無機充填剤Ｂ２の配合量の上限値は、機械的物性が低下することを抑制する点で、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して６０質量部以下とすることが好ましく、より好ましくは５５質量部以下である。 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.
　繊維状無機充填剤Ｂ１及び非繊維状無機充填剤Ｂ２の総含有量は、ポリアリーレンサルファイド樹脂Ａ１００質量部に対して４０質量部以上であることが好ましく、ポリアリーレンサルファイド系樹脂Ａの特性を維持しながら上記無機充填剤Ｂ１，Ｂ２の組み合わせによる作用を発揮させる点で、ポリアリーレンサルファイド樹脂Ａ１００質量部に対して７０質量部以上２２０質量部以下であることがより好ましく、さらに好ましくは、８０質量部以上２００質量部以下である。 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.
（繊維状無機充填剤Ｂ３）
　樹脂組成物は、異径比が２．０以下である繊維状無機充填剤Ｂ３の含有量がポリアリーレンサルファイド系樹脂Ａ１００質量部に対して５０質量部以下である。繊維状無機充填剤Ｂ３の含有量は、３０質量部以下、又は１０質量部未満とすることもできる。繊維状無機充填剤Ｂ３の含有量を５０質量部以下に抑えることで、インサート成形品の成形収縮率及び線膨張係数の異方性をより低下させることができ、その結果高低温衝撃性をより高めることができる。繊維状無機充填剤Ｂ３の含有量は、少ない方が好ましく、実質的に含まないことがより好ましい。「実質的に含まない」とは、樹脂組成物の物性に大きな影響を与えない程度の含有量のことをいい、例えば樹脂組成物中の繊維状無機充填剤Ｂ３の含有量が５質量％以下のことをいい、より好ましくは４質量％以下である。繊維状無機充填剤Ｂ３としては、例えば、長手方向に直角な断面形状が、円形又は略円形である一般的な繊維状の無機充填剤を挙げることができる。繊維状無機充填剤Ｂ３の材料としては、例えば、上記した繊維状無機充填剤Ｂ１の材料と同様のものを挙げることができる。 (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.
（オレフィン系共重合体Ｃ）
　オレフィン系共重合体Ｃは、共重合成分としてα－オレフィン由来の構成単位とα，β－不飽和酸のグリシジルエステル由来の構成単位とを含有する。こうしたオレフィン系共重合体Ｃを含有するので、インサート成形品の高低温衝撃性を著しく高めることができる。オレフィン系共重合体Ｃは、中でも、（メタ）アクリル酸エステル由来の構成単位を含有するオレフィン系共重合体であることが好ましい。オレフィン系共重合体は、１種単独で又は２種以上組み合わせて使用することができる。なお、以下、（メタ）アクリル酸エステルを（メタ）アクリレートともいう。例えば、（メタ）アクリル酸グリシジルエステルをグリシジル（メタ）アクリレートともいう。また、本明細書において、「（メタ）アクリル酸」は、アクリル酸とメタクリル酸との両方を意味し、「（メタ）アクリレート」は、アクリレートとメタクリレートとの両方を意味する。 (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.
　α－オレフィンとしては、特に限定されないが、エチレン、プロピレン、ブチレン等を挙げることができる。中でも、エチレンが好ましい。α－オレフィンは、上記から選ばれる１種又は２種以上を用いることができる。α－オレフィンに由来する共重合成分の含有量は、特に限定されないが、例えば、全樹脂組成物中１質量％以上８質量％以下とすることができる。 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.
　α，β－不飽和酸のグリシジルエステルとしては、例えば、以下の一般式（ＩＩ）に示される構造を有するものを挙げることができる。
Figure JPOXMLDOC01-appb-C000001
 （但し、Ｒ１は、水素又は炭素数１以上１０以下のアルキル基を示す。） Examples of the glycidyl ester of α, β-unsaturated acid include those having a structure represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000001
 (However, R1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.)
　上記一般式（ＩＩ）で示される化合物としては、例えば、アクリル酸グリシジルエステル、メタクリル酸グリシジルエステル（ＧＭＡ）、エタクリル酸グリシジルエステル等を挙げることができる。中でも、メタクリル酸グリシジルエステルが好ましい。α，β－不飽和酸のグリシジルエステルは、１種単独で使用することもでき、２種以上を併用することもできる。α，β－不飽和酸のグリシジルエステルに由来する共重合成分の含有量は、全樹脂組成物中０．０５質量％以上０．６質量％以下であることが好ましい。α，β－不飽和酸のグリシジルエステルに由来する共重合成分の含有量がこの範囲である場合、高低温衝撃性を維持しつつモールドデポジットの析出をより抑制することができる。 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.
　（メタ）アクリル酸エステルとしては、特に限定されないが、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸－ｎ－プロピル、アクリル酸イソプロピル、アクリル酸－ｎ－ブチル、アクリル酸－ｎ－ヘキシル、アクリル酸－ｎ－オクチル、メタクリル酸エステル（例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸－ｎ－プロピル、メタクリル酸イソプロピル、メタクリル酸－ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸－ｎ－アミル、メタクリル酸－ｎ－オクチル）等を挙げることができる。中でも、アクリル酸メチルが好ましい。（メタ）アクリル酸エステルは、１種単独で使用することもでき、２種以上を併用することもできる。（メタ）アクリル酸エステルに由来する共重合成分の含有量は、特に限定されないが、例えば、全樹脂組成物中０．５質量％以上３質量％以下とすることができる。 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.
　α－オレフィン由来の構成単位とα，β－不飽和酸のグリシジルエステル由来の構成単位とを含むオレフィン系共重合体、及び、さらに（メタ）アクリル酸エステル由来の構成単位を含むオレフィン系共重合体は、従来公知の方法で共重合を行うことにより製造することができる。例えば、通常よく知られたラジカル重合反応により共重合を行うことによって、上記オレフィン系共重合体を得ることができる。オレフィン系共重合体の種類は、特に問われず、例えば、ランダム共重合体であっても、ブロック共重合体であってもよい。また、上記オレフィン系共重合体に、例えば、ポリメタアクリル酸メチル、ポリメタアクリル酸エチル、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ブチル、ポリアクリル酸－２エチルヘキシル、ポリスチレン、ポリアクリロニトリル、アクリロニトリル－スチレン共重合体、アクリル酸ブチル－スチレン共重合体等が、分岐状に又は架橋構造的に化学結合したオレフィン系グラフト共重合体であってもよい。 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.
　本実施形態で用いるオレフィン系共重合体は、本発明の効果を害さない範囲で、他の共重合成分由来の構成単位を含有することができる。 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.
　オレフィン系共重合体としては、より具体的には、例えば、グリシジルメタクリレート変性エチレン系共重合体、グリシジルエーテル変性エチレン共重合体等が挙げられ、中でも、グリシジルメタクリレート変性エチレン系共重合体が好ましい。 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.
　グリシジルメタクリレート変性エチレン系共重合体としては、グリシジルメタクリレートグラフト変性エチレン重合体、エチレン－グリシジルメタクリレート共重合体、エチレン－グリシジルメタクリレート－アクリル酸メチル共重合体を挙げることができる。中でも、特に優れた金属樹脂複合成形体が得られることから、エチレン－グリシジルメタクリレート共重合体及びエチレン－グリシジルメタクリレート－アクリル酸メチル共重合体が好ましく、エチレン－グリシジルメタクリレート－アクリル酸メチル共重合体が特に好ましい。エチレン－グリシジルメタクリレート共重合体及びエチレン－グリシジルメタクリレート－アクリル酸メチル共重合体の具体例としては、「ボンドファースト」（住友化学株式会社製）等を挙げることができる。 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.).
　グリシジルエーテル変性エチレン共重合体としては、例えば、グリシジルエーテルグラフト変性エチレン共重合体、グリシジルエーテル－エチレン共重合体を挙げることができる。 Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymer and glycidyl ether-ethylene copolymer.
　オレフィン系共重合体Ｃの含有量は、高低温衝撃性をより高めつつモールドデポジットを抑制する点で、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３質量部以上３０質量部未満であることが好ましく、５質量部以上３０質量部以下、７質量部以上２５質量部以下、又は７質量部以上２０質量部以下とすることができる。 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.
（その他の添加剤等）
　樹脂組成物は、本発明の効果を損なわない範囲で、その目的に応じた所望の特性を付与するために、一般に熱可塑性樹脂及び熱硬化性樹脂に添加される公知の添加剤、即ちバリ抑制剤、離型剤、潤滑剤、可塑剤、難燃剤、染料や顔料等の着色剤、結晶化促進剤、結晶核剤、各種酸化防止剤、熱安定剤、耐候性安定剤、腐食防止剤等を要求性能に応じ配合することが可能である。バリ抑制剤としては、例えば、国際公開第２００６／０６８１６１号や国際公開第２００６／０６８１５９号等に記載されているような、溶融粘度が非常に高い分岐型ポリフェニレンサルファイド系樹脂、シラン化合物等を挙げることができる。シラン化合物としては、ビニルシラン、メタクリロキシシラン、エポキシシラン、アミノシラン、メルカプトシラン等の各種タイプが含まれ、例えばビニルトリクロロシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メルカプトトリメトキシシラン等が例示されるが、これらに限定されるものではない。添加剤の含有量は、例えば、全樹脂組成物中５質量％以下にすることができる。 (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.
　また、樹脂組成物には、その目的に応じ前記成分の他に、他の熱可塑性樹脂成分を補助的に少量併用することも可能である。ここで用いられる他の熱可塑性樹脂としては、高温において安定な樹脂であれば何れのものでもよい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート等の、芳香族ジカルボン酸とジオール、或いはオキシカルボン酸等からなる芳香族ポリエステル、ポリアミド、ポリカーボネート、ＡＢＳ、ポリフェニレンオキサイド、ポリアルキルアクリレート、ポリサルホン、ポリエーテルサルホン、ポリエーテルイミド、ポリエーテルケトン、フッ素樹脂等を挙げることができる。また、これらの熱可塑性樹脂は、２種以上混合して使用することもできる。他の熱可塑性樹脂成分の含有量は、例えば、全樹脂組成物中２０質量％以下、１５質量％以下、又は１０質量％以下にすることができる。 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.
　樹脂組成物の調製は、従来の樹脂組成物調製法として一般に用いられる設備と方法を用いて容易に調製できる。例えば、１）各成分を混合した後、１軸又は２軸の押出機により練り込み押出してペレットを調製し、その後成形する方法、２）一旦組成の異なるペレットを調製し、そのペレットを所定量混合して成形し成形後に目的組成の成形品を得る方法、３）成形機に各成分の１又は２以上を直接仕込む方法等、いずれも使用できる。また、樹脂成分の一部を細かい粉体として、これ以外の成分と混合して添加する方法は、これらの成分の均一配合を図る上で好ましい方法である。 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.
［インサート成形品］
　インサート成形品は、金属、合金又は無機固体物を用いて形成されたインサート部材と、前記インサート部材の表面の少なくとも一部を覆う樹脂部材とを有する。樹脂部材は、上記ポリアリーレンサルファイド系樹脂組成物を用いて形成されたものであり、該樹脂組成物を含む。樹脂部材が上記樹脂組成物を含むので、高低温衝撃性が優れたインサート成形品とすることができる。 [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.
　インサート部材を構成する金属、合金又は無機固体物は、特に限定されないが、成形時に樹脂組成物と接触したとき、変形したり溶融したりしないものが好ましい。例えば、アルミニウム、マグネシウム、銅、鉄等の金属、真鍮等の上記金属の合金、及びガラス、セラミックス等の無機固体物等を挙げることができる。 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.
　インサート成形品の形状及び大きさは、特に限定されず、用途に応じた形状とすることができる。特に、上記した樹脂組成物を含む樹脂部材は、高低温衝撃性が低下しやすい構造を有している場合でも優れた高低温衝撃性を達成することができる。そのため、インサート成形品は、ウェルド部及び応力集中部のいずれか又は両方を有し、ウェルド部及び／又は応力集中部の少なくとも一部の領域の厚さが２ｍｍ以下、又は１．５ｍｍ以下である構造を有していてもよい。 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.
　さらに、インサート成形品は、樹脂部材がウェルド部及び応力集中部の両方を有し、両者が少なくとも一部の領域で一致している構造を有していてもよい。例えば、図１に示すインサート成形品１は、インサート部材１１、及びインサート部材１１の少なくとも一部を全周にわたり覆う樹脂部材１０を有している。インサート部材１１は、二つの側面で形成される角部を有しており、該角部の稜線から樹脂部材１０の側面にわたって応力集中部が形成される。このインサート成形品１１において、樹脂部材１０の、インサート部材１１の角部と接する領域の反対側の領域の側面に、樹脂注入口の痕跡（ゲート痕）が形成されている場合に、樹脂流動末端の接合部であるウェルド部が応力集中部と少なくとも一部の領域で一致する領域に形成される。この場合に得られるインサート成形品１１は、ウェルド部及び応力集中部が少なくとも一部の領域で一致している構造となる。 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.
　なお、「ウェルド部」は、樹脂組成物の流動末端同士が接合（溶接）した部分であり、一般的に他の箇所よりも機械的な強度が劣る傾向にある。そのため、ウェルド部は他の箇所よりも高低温衝撃性が劣る傾向にある。「応力集中部」は、樹脂組成物の膨張収縮により発生する応力が集中する部分であり、例えば、角部（コーナー部）、切り欠き部、傷部、貫通孔、肉抜き部、肉薄部、肉厚変化が大きい箇所及びフローマーク部等を挙げることができる。よって、樹脂部材がウェルド部及び応力集中部の両方を有し、両者が少なくとも一部の領域で一致している、上記した構造を有している場合、通常は高低温衝撃性が顕著に劣ることが想定されるが、本実施形態に係るインサート成形品は、このような構造を有する場合に高低温衝撃性を高める効果がより顕著に発現する。 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.
　インサート成形品は、樹脂部材の樹脂注入口の痕跡がある側の領域の厚さｔ１と、最も肉厚の薄い領域の厚さｔ２との比ｔ１／ｔ２が３以上となる形状を有していてもよい。さらに、インサート成形品は、インサート部材が角部（コーナー部）を有しており、該角部の先端部分の曲率半径ｒが０．８ｍｍ以下、又は０．５ｍｍ以下であってもよい。 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.
　インサート成形品の製造方法は、特に限定されず、例えば、上記した樹脂組成物と予め所望の形状に成形されたインサート部材とをインサート成形することができる。インサート成形は、例えば、金型にインサート部材を予め装着し、その外側に上記樹脂組成物を射出成形又は押出圧縮成形等により充填して複合成形することができる。 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.
　以下に実施例を示して本発明を更に具体的に説明するが、これらの実施例により本発明の解釈が限定されるものではない。 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.
［実施例１～９、比較例１～４］
　以下に示す材料を用いて、表１，２に示す組成及び含有割合で、ポリアリーレンサルファイド系樹脂、繊維状無機充填剤、非繊維状無機充填剤及びオレフィン系共重合体をドライブレンドした。これをシリンダー温度３２０℃の二軸押出機に投入して溶融混練することで、実施例及び比較例の樹脂組成物ペレットを得た。 [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.
（ポリアリーレンサルファイド系樹脂）
　ポリアリーレンサルファイド系樹脂Ａ：ポリフェニレンサルファイド樹脂（ＰＰＳ）、株式会社クレハ製「フォートロンＫＰＳ」（溶融粘度：２０Ｐａ・ｓ（せん断速度：１２１６ｓｅｃ－１、３１０℃）） (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.))
（ポリアリーレンサルファイド系樹脂の溶融粘度の測定）
　上記ポリアリーレンサルファイド系樹脂Ａの溶融粘度は以下のようにして測定した。
　東洋精機製作所製キャピログラフを用い、キャピラリーとして１ｍｍφ×２０ｍｍＬ／フラットダイを使用し、バレル温度３１０℃、せん断速度１２１６ｓｅｃ－１での溶融粘度を測定した。 (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.
（無機充填剤）
　繊維状無機充填剤Ｂ１：ガラス繊維、断面が長円形、長径２８μｍ、短径７μｍ、長径／短径の比４．０、日東紡績株式会社製「異形断面チョップドストランド　ＣＳＧ　３ＰＡ－８３０」
　非繊維状無機充填剤Ｂ２：炭酸カルシウム、平均粒子径（５０％ｄ）２５μｍ、旭鉱末株式会社製「ＭＣ－３５Ｗ」
　非繊維状無機充填剤Ｂ２：ガラスビーズ、平均粒子径（５０％ｄ）２０μｍ、ポッターズ・バロティーニ株式会社製「ＥＧＢ７３１Ａ」
　非繊維状無機充填剤Ｂ２：ガラスフレーク、平均粒子径（５０％ｄ）６００μｍ、日本板硝子株式会社製「ＲＥＦＧ－１０８」
　繊維状無機充填剤Ｂ３：ガラス繊維、断面がまゆ形、長径２４μｍ、短径１２μｍ、長径／短径の比２．０、日東紡績株式会社製「異形断面チョップドストランド　ＣＳＨ　３ＰＡ－８６０」 (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”
（オレフィン系共重合体）
　オレフィン系共重合体Ｃ：住友化学株式会社製「ボンドファースト７Ｍ」、共重合成分として、エチレンを６７質量％、メタクリル酸グリシジルエステルを６質量％、及びアクリル酸メチルを２７質量％含む。 (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.
［評価］
（高低温衝撃性）
　樹脂組成物と金属製のインサート部材とを用い、射出成形により図１～図３に示す試験片をインサート成形し、高低温衝撃性を評価した。図１は、インサート成形した試験片１を示す図であり、図２は、インサート部材１１を示す図であり、図３は、試験片１の寸法を示す図である。試験片１は、図１に示すように、樹脂組成物からなる円柱形の樹脂部材１０に金属製のインサート部材１１が埋入した状態で成形されている。円柱形の樹脂部材１０は、上記のようにして得られたペレットを用いて成形されたものである。インサート部材１１は、図２に示すように、柱状であって、その上面及び底面の形状が、一側が円弧形状、他側が鋭角形状の涙型の形状をなす。鋭角形状部分は、部分拡大図である図２（ｂ）に示すように、先端は円弧状になっており、この曲率半径ｒは０．２ｍｍである。また、インサート部材１１は、円柱形の樹脂部材１０の高さよりも高く、その一部が突出している（図１（ａ）参照）。さらに、図３（ａ）に示すように、インサート部材１１の円弧を一部とする円の中心Ｏ１と、樹脂部材１０の円の中心Ｏ２とは一致せず、インサート部材１１の鋭角形状側が樹脂部材１０の側面に近接するように配置されている。そして、インサート部材１１の鋭角形状の先端と、樹脂部材１０の側面との距離ｄｗは１ｍｍであり、樹脂部材１０において、インサート部材１１の鋭角形状の先端近傍が応力集中部を形成しており、かつ肉厚が最も薄い領域となっている。なお、図３に、試験片の寸法について数値を示しているが、その単位はｍｍである。試験片１において、樹脂注入口の痕跡（ゲート痕）は、インサート部材１１の鋭角形状に最も近い側面の反対側の側面に形成されている。この場合、インサート部材１１の鋭角形状に最も近い側面にウェルド部が形成されている。 [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.
　上記の試験片に対し、冷熱衝撃試験機（エスペック株式会社製）を用い、－４０℃にて１．５時間冷却後、１８０℃にて１．５時間加熱するというサイクルを繰り返し、２０サイクル毎にウェルド部を観察した。ウェルド部にクラックが発生したときのサイクル数を高低温衝撃性の指標として評価した。結果を表１，２に示す。サイクル数が２３０以上である場合に高低温衝撃性が優れており、２６０以上である場合に高低温衝撃性が特に優れている。 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.
（低反り性）
　実施例及び比較例で得られた樹脂組成物を用いて、射出成形によりシリンダー温度３２０℃、金型温度１５０℃、保圧力７０ＭＰａの条件で、８０ｍｍ×８０ｍｍ×厚さ１．５ｍｍの平板状樹脂成形品２を５枚作製した。１枚目の平板状樹脂成形品２を水平面に静置し、株式会社ミツトヨ製のＣＮＣ画像測定機（型式：ＱＶＢＨＵ４０４－ＰＲＯ１Ｆ）を用いて、上記平板状樹脂成形品２上の９箇所において、上記水平面からの高さを測定し、得られた測定値から平均の高さを算出した。図４中に黒丸で高さを測定した位置を示す（ｄ１＝３ｍｍ、ｄ２＝３７ｍｍ）。上記水平面からの高さが上記平均の高さと同一であり上記水平面と平行な面を基準面とした。上記９箇所で測定された高さから、基準面からの最大高さと最小高さとを選択し、両者の差を算出した。同様にして、他の４枚の平板状樹脂成形品についても上記の差を算出し、得られた５個の値を平均して、反り量の値とした。結果を表１，２に示す。反り量が少ない程、低反り性が優れている。 (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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
１　　試験片
２　　平板状樹脂成形品
１０　樹脂部材
１１　インサート部材
１００　成形品 DESCRIPTION OF SYMBOLS 1 Test piece 2 Flat resin molded product 10 Resin member 11 Insert member 100 Molded product

Claims (10)

  1. 　ポリアリーレンサルファイド系樹脂Ａ、長手方向に直角な断面の長径と短径との比である異径比が３．０以上である繊維状無機充填剤Ｂ１、非繊維状無機充填剤Ｂ２、及びα－オレフィン由来の構成単位とα，β－不飽和酸のグリシジルエステル由来の構成単位とを含有するオレフィン系共重合体Ｃを含有し、
    　繊維状無機充填剤Ｂ１及び非繊維状無機充填剤Ｂ２の質量比Ｂ１／Ｂ２が１．０を超え、
    　長手方向に直角な断面の長径と短径との比である異径比が２．０以下である繊維状無機充填剤Ｂ３の含有量がポリアリーレンサルファイド系樹脂Ａ１００質量部に対して５０質量部以下である、ポリアリーレンサルファイド系樹脂組成物。     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.
  2. 　繊維状無機充填剤Ｂ１の含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３０質量部以上８０質量部以下である、請求項１に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  3. 　非繊維状無機充填剤Ｂ２の含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して２０質量部以上６０質量部以下である、請求項１又は２に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  4. 　非繊維状無機充填剤Ｂ２の平均粒子径が１０μｍ以上である、請求項１から３のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  5. 　非繊維状無機充填剤Ｂ２が粉粒状無機充填材を含む、請求項１から４のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  6. 　非繊維状無機充填剤Ｂ２が炭酸カルシウム及びガラスビーズのいずれか又は両方を含む、請求項１から５のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  7. 　オレフィン系共重合体Ｃの含有量が、ポリアリーレンサルファイド系樹脂Ａ１００質量部に対して３質量部以上３０質量部以下である、請求項１から６のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物。 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.
  8. 　繊維状無機充填剤Ｂ３を実質的に含まない、請求項１から７のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物。 The polyarylene sulfide-based resin composition according to any one of claims 1 to 7, which is substantially free of fibrous inorganic filler B3.
  9. 　金属、合金又は無機固体物を用いて形成されたインサート部材と、前記インサート部材の表面の少なくとも一部を覆う樹脂部材とを有し、前記樹脂部材が請求項１から８のいずれか一項に記載のポリアリーレンサルファイド系樹脂組成物を用いて形成されたことを特徴とする、インサート成形品。 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.
  10. 　前記樹脂部材が、前記樹脂組成物の流動末端同士が接合したウェルド部、及び膨張収縮により発生する応力が集中する応力集中部のいずれか又は両方を有し、前記ウェルド部及び／又は前記応力集中部の少なくとも一部の領域の厚さが２ｍｍ以下である、請求項９に記載のインサート成形品。 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.
PCT/JP2018/015670 2017-04-27 2018-04-16 Poly(arylene sulfide) resin composition and insert-molded article WO2018198850A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-088302 2017-04-27
JP2017088302A JP2020109135A (en) 2017-04-27 2017-04-27 Polyarylene sulfide-based resin composition and insert molding

Publications (1)

Publication Number Publication Date
WO2018198850A1 true WO2018198850A1 (en) 2018-11-01

Family

ID=63918323

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/015670 WO2018198850A1 (en) 2017-04-27 2018-04-16 Poly(arylene sulfide) resin composition and insert-molded article

Country Status (2)

Country Link
JP (1) JP2020109135A (en)
WO (1) WO2018198850A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019208708A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
WO2019208709A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
WO2019208706A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
WO2020196273A1 (en) * 2019-03-27 2020-10-01 東レ株式会社 Polyphenylene sulfide resin composition and molded article
JP2021017493A (en) * 2019-07-19 2021-02-15 帝人株式会社 Resin composition

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02173047A (en) * 1988-12-26 1990-07-04 Polyplastics Co Fiber-reinforced thermoplastic resin composition
JP2005161693A (en) * 2003-12-03 2005-06-23 Polyplastics Co Insert molded product
WO2014103814A1 (en) * 2012-12-27 2014-07-03 ポリプラスチックス株式会社 Resin composition and tabular insert-molded body
JP2015101628A (en) * 2013-11-22 2015-06-04 東ソー株式会社 Polyarylene sulfide-based composition
WO2015146718A1 (en) * 2014-03-27 2015-10-01 ポリプラスチックス株式会社 Polyarylene sulfide resin composition and insert-molded body
JP2016069459A (en) * 2014-09-29 2016-05-09 東ソー株式会社 Polyarylene sulfide resin composition
WO2016153048A1 (en) * 2015-03-26 2016-09-29 住友化学株式会社 Ovenware, and resin composition for molding ovenware
JP2016535147A (en) * 2013-08-22 2016-11-10 東レ株式会社 Polyphenylene sulfide resin composition, molded product thereof and method for producing the molded product
JP2017088690A (en) * 2015-11-06 2017-05-25 東ソー株式会社 Polyarylene sulfide-based composition
JP2017088691A (en) * 2015-11-06 2017-05-25 東ソー株式会社 Polyarylene sulfide-based composition
JP2017101167A (en) * 2015-12-03 2017-06-08 東ソー株式会社 Polyarylene sulfide composition

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02173047A (en) * 1988-12-26 1990-07-04 Polyplastics Co Fiber-reinforced thermoplastic resin composition
JP2005161693A (en) * 2003-12-03 2005-06-23 Polyplastics Co Insert molded product
WO2014103814A1 (en) * 2012-12-27 2014-07-03 ポリプラスチックス株式会社 Resin composition and tabular insert-molded body
JP2016535147A (en) * 2013-08-22 2016-11-10 東レ株式会社 Polyphenylene sulfide resin composition, molded product thereof and method for producing the molded product
JP2015101628A (en) * 2013-11-22 2015-06-04 東ソー株式会社 Polyarylene sulfide-based composition
WO2015146718A1 (en) * 2014-03-27 2015-10-01 ポリプラスチックス株式会社 Polyarylene sulfide resin composition and insert-molded body
JP2016069459A (en) * 2014-09-29 2016-05-09 東ソー株式会社 Polyarylene sulfide resin composition
WO2016153048A1 (en) * 2015-03-26 2016-09-29 住友化学株式会社 Ovenware, and resin composition for molding ovenware
JP2017088690A (en) * 2015-11-06 2017-05-25 東ソー株式会社 Polyarylene sulfide-based composition
JP2017088691A (en) * 2015-11-06 2017-05-25 東ソー株式会社 Polyarylene sulfide-based composition
JP2017101167A (en) * 2015-12-03 2017-06-08 東ソー株式会社 Polyarylene sulfide composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019208708A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
WO2019208709A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
WO2019208706A1 (en) * 2018-04-27 2019-10-31 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert-molded product
JPWO2019208706A1 (en) * 2018-04-27 2020-04-30 ポリプラスチックス株式会社 Polyarylene sulfide-based resin composition and insert molded article
JPWO2019208708A1 (en) * 2018-04-27 2020-05-07 ポリプラスチックス株式会社 Polyarylene sulfide resin composition and insert molded article
US11091635B1 (en) 2018-04-27 2021-08-17 Polyplastics Co., Ltd. Polyarylene sulfide-based resin composition and insert-molded product
WO2020196273A1 (en) * 2019-03-27 2020-10-01 東レ株式会社 Polyphenylene sulfide resin composition and molded article
CN113557266A (en) * 2019-03-27 2021-10-26 东丽株式会社 Polyphenylene sulfide resin composition and molded article
JP2021017493A (en) * 2019-07-19 2021-02-15 帝人株式会社 Resin composition

Also Published As

Publication number Publication date
JP2020109135A (en) 2020-07-16

Similar Documents

Publication Publication Date Title
WO2018198850A1 (en) Poly(arylene sulfide) resin composition and insert-molded article
WO2018079704A1 (en) Poly(arylene sulfide)-based resin composition and insert-molded article
WO2018105437A1 (en) Poly(arylene sulfide) resin composition and insert-molded article
EP3239240B1 (en) Polyarylene sulfide resin composition and insert molded article
WO2019208709A1 (en) Polyarylene sulfide-based resin composition and insert-molded product
WO2019208708A1 (en) Polyarylene sulfide-based resin composition and insert-molded product
JP2020084027A (en) Polyarylene sulfide resin composition and manufacturing method therefor
WO2019208706A1 (en) Polyarylene sulfide-based resin composition and insert-molded product
KR20150023780A (en) Light-reflecting component and method for producing same
JP2019183156A (en) Polyarylene sulfide resin composition and insert molded article
WO2019026869A1 (en) Polyarylene sulfide resin composition and fuel contact body
JP6392998B2 (en) Polyarylene sulfide-based resin composition and insert molded product
JP7465639B2 (en) Polyarylene sulfide resin molded products
JP2020105502A (en) Polyarylene sulfide resin composition and molded product thereof
JP7382541B2 (en) Polyarylene sulfide resin composition and insert molded products
JP6993390B2 (en) Casing member for in-vehicle camera and its manufacturing method
JP6387211B1 (en) Polyarylene sulfide resin composition
JP2007137983A (en) Polyarylene sulfide resin composition for molded article having cylindrical part
JP6167011B2 (en) Electrically insulating high thermal conductive resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18792139

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18792139

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP