[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2020054772A1 - Composition de résine de poly(sulfure d'arylène), article moulé et article moulé par insertion - Google Patents

Composition de résine de poly(sulfure d'arylène), article moulé et article moulé par insertion Download PDF

Info

Publication number
WO2020054772A1
WO2020054772A1 PCT/JP2019/035732 JP2019035732W WO2020054772A1 WO 2020054772 A1 WO2020054772 A1 WO 2020054772A1 JP 2019035732 W JP2019035732 W JP 2019035732W WO 2020054772 A1 WO2020054772 A1 WO 2020054772A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
resin composition
olefin
polyarylene sulfide
sulfide resin
Prior art date
Application number
PCT/JP2019/035732
Other languages
English (en)
Japanese (ja)
Inventor
博樹 荒井
大西　克平
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 WO2020054772A1 publication Critical patent/WO2020054772A1/fr

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
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K11/00—Arrangement in connection with cooling of propulsion units
    • B60K11/02—Arrangement in connection with cooling of propulsion units with liquid cooling
    • B60K11/04—Arrangement or mounting of radiators, radiator shutters, or radiator blinds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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 comprises a polyarylene sulfide resin, a polyarylene sulfide resin composition used for molding a molded article that can be brought into contact with a fluid containing water, a molded article obtained by molding the resin composition, and the resin composition
  • the present invention relates to an insert molded product formed by insert molding using an insert member.
  • PAS resin polyarylene sulfide resin
  • PPS resin polyphenylene sulfide resin
  • Patent Document 3 proposes a PAS resin composition having heat shock resistance and high fluidity during melting.
  • the PAS resin composition contains a PAS resin having a predetermined melt viscosity and a predetermined elastomer, and defines a predetermined fluidity. This PAS resin composition can satisfy the requirements for heat shock resistance and high fluidity.
  • LLC long life coolant
  • an electric water pump a fluid containing water and an organic solvent component such as ethylene glycol or glycerin.
  • a PAS resin composition is used as a sealing material for protecting a yoke having a magnetic material from the LLC. May be used.
  • heat shock resistance in an environment where LLC can come into contact cannot be considered in the same manner as heat shock resistance in a dry environment as described above. In other words, in the presence of such a fluid containing water, not only a temperature change but also durability against hot water is required, and a higher level of performance than heat shock resistance in a dry environment is required.
  • a member such as a yoke has a thin portion of, for example, about 1 mm. In order to form such a thin portion, high fluidity is required at the time of melting.
  • the PAS resin composition described in Patent Literature 3 has heat shock resistance and high fluidity, but does not consider heat shock resistance in an environment where a fluid containing water can come into contact with it, and there is room for improvement. Was left.
  • the present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a polyarylene sulfide resin composition having excellent heat shock resistance and fluidity during melting in an environment where it can come into contact with a fluid containing water. Object, molded article, and insert molded article.
  • the content ratio of the constituent unit derived from the glycidyl ester of the ⁇ , ⁇ -unsaturated acid to the olefin-based copolymer is 1.0 to 8.0% by mass,
  • a polyarylene sulfide resin composition having a flow length of 110 to 300 mm with a width of 20 mm and a thickness of 1 mm at a cylinder temperature of 320 ° C., an injection pressure of 100 MPa, a holding pressure of 100 MPa, and a mold temperature of 150 ° C.
  • a polyarylene sulfide resin composition a molded article, and an insert molded article that are excellent in heat shock resistance and fluidity during melting in an environment where the composition can come into contact with a fluid containing water.
  • FIG. 1 is a view showing a test piece used in a heat shock resistance test, in which (a) is a perspective view and (b) is a plan view.
  • 2A and 2B are diagrams illustrating an insert member of the test piece illustrated in FIG. 1, wherein FIG. 2A is a perspective view, and FIG. 2B is an enlarged plan view of an acute angle portion.
  • 3A and 3B are explanatory diagrams illustrating dimensions of the test piece illustrated in FIG. 1, wherein FIG. 3A is a plan view and FIG. 3B is a side view.
  • the PAS resin composition of the present embodiment is a PAS resin composition used for molding a molded article that can come into contact with a fluid containing water, and has a melt viscosity of 100 to 250 Pa measured at a temperature of 310 ° C. and a shear rate of 1200 sec ⁇ 1.
  • An olefin copolymer containing a structural unit derived from an ⁇ -olefin and a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid is used in an amount of from 2.0 to 9.
  • the width is 20 mm and the thickness is 1 m at a cylinder temperature of 320 ° C., an injection pressure of 100 MPa, a holding pressure of 100 MPa, and a mold temperature of 150 ° C. It is characterized in that the flow length is 110 ⁇ 300 mm.
  • the PAS resin composition of the present embodiment contains a predetermined amount of a predetermined olefin-based copolymer, glass fiber, and a silane coupling agent with respect to a PAS resin having a predetermined melt viscosity, thereby forming a fluid containing water.
  • the heat shock resistance (hereinafter, also referred to as “LLC resistance”) in an environment where it can come into contact, and the fluidity during melting are improved.
  • heat shock resistance can be improved by using an olefin polymer (elastomer) in the PAS resin composition, but it is not possible to improve LLC resistance alone. Therefore, in the present embodiment, the use of glass fibers and a silane coupling agent in predetermined amounts improves the LLC resistance.
  • the present inventors when improving the LLC resistance, the effect is expressed by simply reducing the content of the glass fiber to an amount that simply improves the heat shock resistance, and conversely, exceeds a certain amount. And found that the effect was inferior. Therefore, by limiting the range of the glass fiber content to the above range, the LLC resistance is improved. Although the resistance to LLC can be improved even when the content of the silane coupling agent is relatively large, the use of a large amount of the silane coupling agent increases the viscosity at the time of melting, thereby lowering the fluidity. Therefore, by defining the range of the content of the silane coupling agent in the above range, both the improvement of LLC resistance and the high fluidity at the time of melting are achieved.
  • the PAS resin composition of the present embodiment exhibits high fluidity at the time of melting by using a PAS resin having a relatively low melt viscosity and defining an index for a prescribed fluidity under a prescribed condition.
  • the olefin-based copolymer by specifying the ratio of the constituent units derived from the glycidyl ester of an ⁇ , ⁇ -unsaturated acid, the fluidity is improved in addition to the heat shock resistance.
  • the PAS resin composition of the present embodiment by defining each component as described above, the LLC resistance and the fluidity during melting are excellent. First, each component of the PAS resin composition will be described.
  • PAS resins are characterized by excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties, and good workability.
  • the PAS resin is a polymer compound mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit.
  • a PAS resin having a molecular structure generally known is used. Can be used.
  • arylene group examples include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, p, p′- Examples include a diphenylene ether group, a p, p'-diphenylenecarbonyl group, and a naphthalene group.
  • the PAS resin may be a homopolymer composed of only the above-mentioned repeating units, or a copolymer containing the following different types of repeating units may be preferable in terms of processability and the like.
  • a polyphenylene sulfide resin having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group is preferably used.
  • the copolymer two or more different combinations among the above-mentioned arylene sulfide groups composed of an arylene group can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used.
  • PAS resins those containing a p-phenylene sulfide group in an amount of 70 mol% or more, preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.
  • PAS resins a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used.
  • the PAS resin used in the present embodiment may be a mixture of two or more different molecular weight PAS resins.
  • a partially branched or crosslinked structure is formed by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents at the time of condensation polymerization.
  • a monomer such as a polyhalo aromatic compound having three or more halogen substituents
  • the melt viscosity (310 ° C., shear rate 1200 sec ⁇ 1 ) of the PAS resin as the base resin used in the present embodiment is 100 to 250 Pa ⁇ s including the case of the above mixed system. If the melt viscosity is less than 100 Pa ⁇ s, the LLC resistance is poor, and if it exceeds 250 Pa ⁇ s, the fluidity is poor.
  • the melt viscosity is preferably from 110 to 240 Pa ⁇ s, more preferably from 130 to 200 Pa ⁇ s.
  • the method for producing the PAS resin is not particularly limited, and it can be produced by a conventionally known production method. For example, it can be produced by synthesizing a low molecular weight PAS resin and then polymerizing it at a high temperature in the presence of a known polymerization aid to increase the molecular weight.
  • the PAS resin composition of the present embodiment may contain other resin components in addition to the above-described PAS resin as a resin component as long as the effect is not impaired.
  • Other resin components are not particularly limited, for example, polyethylene resin, polypropylene resin, polyamide resin, polyacetal resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, polyamide imide Resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, liquid crystal resin, fluorine resin, cyclic olefin resin (cyclic olefin polymer, cyclic olefin copolymer, etc.), thermoplastic Elastomers (however, those other than the olefin-based copolymer described later), silicone-based polymers, various biodegradable resins, and the like can be used.
  • two or more resin components may be used in combination.
  • polybutylene terephthalate resin, polyacetal resin, liquid crystal resin and the like are preferably used from the viewpoint of mechanical properties, electrical properties, physical / chemical properties, workability and the like.
  • the olefin-based copolymer is used for improving heat shock resistance, and includes a constituent unit derived from ⁇ -olefin and a constituent unit derived from ⁇ , ⁇ -unsaturated glycidyl ester.
  • the olefin-based copolymer can be used alone or in combination of two or more.
  • each structural unit will be described.
  • the (meth) acrylate 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 restricted but includes, for example, ethylene, propylene, butylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene And the like, and ethylene is particularly preferred.
  • the ⁇ -olefins can be used alone or in combination of two or more.
  • 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 entire PAS resin composition.
  • the olefin-based copolymer contains a constituent unit derived from ⁇ -olefin as a copolymer component, flexibility is easily imparted to the resin member.
  • the softening of the resin member by imparting flexibility contributes to the improvement of heat shock resistance.
  • the glycidyl ester of an ⁇ , ⁇ -unsaturated acid is not particularly limited, and examples thereof include those having a structure represented by the following general formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and the like can be mentioned, and glycidyl methacrylate is particularly preferable.
  • the glycidyl esters of ⁇ , ⁇ -unsaturated acids can be used alone or in combination of two or more.
  • the content ratio of the constituent unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid to the olefin-based copolymer is 1.0 to 8.0% by mass. It is difficult to form an inferior thin portion, and if it is less than 1.0% by mass, the effect of heat shock resistance becomes insufficient.
  • the content ratio is preferably 2.0 to 7.0% by mass, and more preferably 2.5 to 6.5% by mass.
  • the content ratio of the structural unit derived from the glycidyl ester of the ⁇ , ⁇ -unsaturated acid to the olefin copolymer when two or more olefin copolymers are used in combination is based on the ratio of ⁇ , ⁇ -to the total amount of the olefin copolymer after mixing. It is a content ratio of a structural unit derived from a glycidyl ester of an unsaturated acid.
  • the olefin-based copolymer in order to further improve the heat shock resistance, preferably further contains a structural unit derived from a (meth) acrylate.
  • the (meth) acrylate is not particularly restricted but includes, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, acrylic Acrylic esters such as isobutyl acrylate, n-amyl acrylate, n-octyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid And methacrylic esters such as -n-hexyl, isobutyl methacrylate, n-amyl methacrylate, and n-octyl methacrylate.
  • (Meth) acrylic acid esters can be used alone or in combination of two or more.
  • the content of the copolymer component derived from the (meth) acrylic acid ester is not particularly limited, but can be, for example, 0.5% by mass or more and 3% by mass or less in the entire PAS resin composition.
  • the olefin copolymer can be produced by copolymerization by a conventionally known method.
  • the above-mentioned olefin-based copolymer can be obtained by performing copolymerization by a generally well-known radical polymerization reaction.
  • the type of the olefin-based copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer.
  • the above-mentioned olefin-based copolymer includes, for example, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly (2-ethylhexyl acrylate), polystyrene, polyacrylonitrile ,
  • An acrylonitrile-styrene copolymer, a butyl acrylate-styrene copolymer, or the like may be an olefin-based graft copolymer chemically bonded in a branched or cross-linked structure.
  • the olefin copolymer used in the present embodiment may contain structural units derived from other copolymer components as long as the effect is not impaired.
  • examples of the olefin copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate Copolymers, ethylene-glycidyl methacrylate-propyl acrylate copolymer, ethylene-glycidyl methacrylate-butyl acrylate copolymer, and the like.
  • ethylene-glycidyl methacrylate copolymer and ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is particularly preferable.
  • 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.).
  • the content of the olefin copolymer is 2.0 to 9.0 parts by mass based on 100 parts by mass of the PAS resin, and the balance between the heat shock resistance and the fluidity.
  • 2.0 to 7.0 parts by mass is preferable, and 2.0 to 5.0 parts by mass is more preferable.
  • the PAS resin composition of the present embodiment in order to further improve the fluidity, a constitutional unit derived from an ethylene / ⁇ -olefin copolymer and an ⁇ -olefin and an alkyl ester derived from an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester are used. It is preferable that the composition further contains at least one olefin copolymer selected from the group consisting of olefin copolymers containing a structural unit.
  • olefin-based copolymers examples include copolymers of ethylene and an ⁇ -olefin having 3 or more carbon atoms, such as ethylene / propylene copolymer, ethylene / 1-butene copolymer, and ethylene / octene copolymer. And a copolymer of ethylene and an alkyl (meth) acrylate such as an ethylene / ethyl acrylate copolymer (EEA) and an ethylene / methacrylic acid copolymer.
  • ESA ethylene / ethyl acrylate copolymer
  • the content of the olefin copolymer is preferably from 0 to 10 parts by mass based on 100 parts by mass of the PAS resin.
  • the PAS resin composition of the present embodiment contains glass fibers, the amount of addition is most important for improving LLC resistance. That is, by including 5 to 40 parts by mass of glass fiber with respect to 100 parts by mass of PAS resin, LLC resistance can be improved. If the glass fiber content is less than 5 parts by mass, the LLC resistance cannot be improved, and if it exceeds 40 parts by mass, the fluidity is poor and the LLC resistance cannot be improved.
  • the glass fiber preferably contains 7 to 35 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the PAS resin.
  • the fiber diameter of the glass fiber is not particularly limited, but may be, for example, 5 ⁇ m or more and 30 ⁇ m or less in the initial shape (shape before melt kneading).
  • the fiber diameter of the glass fiber refers to the major diameter of the fiber cross section of the glass fiber.
  • the cross-sectional shape of the glass fiber may be, for example, a perfect circle, an ellipse, or the like.
  • the type of glass fiber is not particularly limited, and for example, A glass, C glass, E glass, or the like can be used. Among them, E glass (alkali-free glass) is preferably used.
  • the glass fiber may or may not have been subjected to a surface treatment. Examples of the surface treatment for the glass fiber include a treatment with an epoxy-based, acrylic, urethane-based coating or sizing agent, and a treatment with a silane coupling agent such as aminosilane or epoxysilane.
  • chopped glass fibers obtained by cutting a large number of these fibers into a predetermined length.
  • the cut length of the chopped glass fiber is not particularly limited, and may be, for example, about 1 to 10 mm.
  • the silane coupling agent is used for improving LLC resistance.
  • the content of the silane coupling agent is 0.1 to 0.7 part by mass, preferably 0.1 to 0.5 part by mass, per 100 parts by mass of the PAS resin. If the content is less than 0.1 part by mass, the LLC resistance cannot be improved, and if it exceeds 0.7 part by mass, the viscosity increases and the fluidity decreases.
  • silane coupling agent those having a functional group (for example, vinylalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, allylalkoxysilane, aminosilane, etc.) can exert the effects of the present embodiment. Coupling agents are preferred.
  • the aminosilane coupling agent refers to a compound containing a silicon atom to which an alkoxy group is bonded in one molecule and a functional group containing a nitrogen atom.
  • Specific aminosilane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (triethoxysilyl) propyl ] Ethylenediamine, N, N'-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N'-bis [3- (Triethoxysily
  • aminosilane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, and N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane are preferred, and ⁇ -aminopropyltrimethoxysilane and More preferably, ⁇ -aminopropyltriethoxysilane is used.
  • silane coupling agents may be used alone or in combination of two or more.
  • the PAS resin composition of the present embodiment can be a lubricant, a nucleating agent, a flame retardant, a flame retardant aid, an antioxidant, a metal deactivator, other anti-aging agents, a UV absorber, Agent, plasticizer, pigment, dye, colorant, antistatic agent, foaming agent, glass beads, silica, calcium carbonate, talc, glass flake, kaolin, clay, alumina, aluminum nitride, nitride such as boron nitride Fillers; hardly soluble ionic crystal particles such as barium sulfate, calcium fluoride, barium fluoride; fillers using semiconductor materials (elemental semiconductors such as Si, Ge, Se, Te; compound semiconductors such as oxide semiconductors); A filler, a conductive filler, or the like may be contained.
  • PAS resin composition of the present embodiment can be manufactured by melt-kneading a mixed component containing at least a PAS resin, an olefin-based copolymer, a glass fiber, and a silane coupling agent.
  • the method for producing the PAS resin composition of the present embodiment is not particularly limited, and various methods known in the art can be employed. For example, there is a method in which the above-described components are mixed, then put into an extruder, melt-kneaded, and pelletized.
  • a method of once preparing pellets having different compositions, mixing a predetermined amount of the pellets, subjecting the mixture to molding, and obtaining a molded article of a desired composition after molding, a method of directly charging one or more of each component to a molding machine, and the like. May be used.
  • the PAS resin composition of the present embodiment can be prepared by being put into an extruder, melt-kneaded, and pelletized, and then put into an injection molding machine equipped with a predetermined mold and injection-molded. it can.
  • the PAS resin composition of the present embodiment has a flow length of 110 mm to 300 mm with a width of 20 mm and a thickness of 1 mm at a cylinder temperature of 320 ° C., an injection pressure of 100 MPa, a holding pressure of 100 MPa, and a mold temperature of 150 ° C.
  • the flow length is 110 mm or more and 300 mm or less, it can be said that the fluidity is good, and it is possible to satisfactorily mold a thin resin portion in a complicated structure without excessively increasing the molding temperature.
  • the PAS resin composition of the present embodiment can be molded satisfactorily even when the thickness of a molded article requiring high fluidity at the time of melting is as thin as about 1 mm, as shown in Examples described later. .
  • the flow length of the PAS resin composition is preferably from 120 mm to 300 mm, more preferably from 130 mm to 300 mm.
  • the shape of the PAS resin molded product is not particularly limited and can be appropriately selected depending on the application.
  • it can be formed into a three-dimensional molded body having a desired shape in addition to a sheet shape, a plate shape, a tubular shape, a film shape, and the like.
  • the PAS resin composition of the present embodiment is used for molding a molded article that can come into contact with a fluid containing water.
  • the fluid containing water include an organic solvent component such as ethylene glycol and glycerin, and water. And so-called long life coolant (LLC), and a washer liquid.
  • LLC long life coolant
  • the molded article of the present embodiment is formed by molding the above-described PAS resin composition. That is, the molded article of the present embodiment can be suitably used as a member having a thin portion, which requires heat shock resistance, particularly LLC resistance. Examples of such a member include a yoke, an impeller, a radiator tank, a thermostat housing, a flow shut valve, a cooling water control valve, and various pipes used in the above-described electric water pump.
  • the PAS resin composition of the present embodiment Since the PAS resin composition of the present embodiment has high fluidity at the time of melting, the PAS resin composition spreads to a thin portion having a thickness of 1.0 mm or less in a mold at the time of molding, and the thin portion can be favorably molded. . Therefore, the PAS resin composition of the present embodiment can favorably mold even a molded article having a thin portion having a thickness of 1.0 mm or less at least in part.
  • the thin portion may be formed at a pinpoint on a part of the molded product, or may be formed in a region occupying most of the molded product.
  • the insert molded product of the present embodiment has an insert member and a resin member that covers at least a part of the insert member.
  • the resin member is formed using the above-described PAS resin composition, and includes the PAS resin composition.
  • the insert molded product of the present embodiment is a composite molded product in which an insert member such as a metal is previously mounted on a molding die, and the PAS resin composition of the present embodiment is filled in the molding die. is there.
  • As a molding method for filling the PAS resin composition into a mold there are an injection method, an extrusion compression molding method and the like, and an injection molding method is generally used.
  • the material of the insert member is used for the purpose of making the most of its properties and compensating for the drawbacks of the PAS resin composition, when it comes into contact with the PAS resin composition during molding, it does not change its shape or melt. Things are used. For this reason, metals such as aluminum, magnesium, copper, iron, brass and their alloys, and inorganic solids such as glass and ceramics, which are preliminarily formed into plates, rods, pins, screws, etc., are used. You.
  • the insert molded product of the present embodiment is also a member requiring heat shock resistance, particularly LLC resistance, similarly to the molded product of the present embodiment, and is a member having a thin portion in at least a part of the resin member. It can be suitably used.
  • the resin member tends to be necessarily thinner due to the presence of the insert member, and there may be a thin portion that is difficult to mold.
  • the insert molded product of the present embodiment forms the resin member using the PAS resin composition of the present embodiment having high fluidity at the time of melting, even if there is a portion where the resin member becomes thin, it can be satisfactorily formed. Can be molded.
  • the insert molded product of the present embodiment may have a thin portion having a thickness of 1.0 mm or less on at least a part of the resin member.
  • the thickness of the thin portion indicates the thickness of only the PAS resin composition portion where the PAS resin composition and the insert member are in contact, and does not include the thickness of the insert member itself.
  • each raw material component was introduced from a raw material supply section (hopper) of a twin-screw extruder having a cylinder temperature of 320 ° C. (glass fiber was supplied from a side feed section of the extruder. The mixture was melt-kneaded under the conditions of an extrusion rate of 20 kg / Hr and a screw rotation speed of 200 rpm, and pelletized. Details of each raw material component shown in Table 1 are described below.
  • melt viscosity of PPS resin was measured as follows. The melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1200 sec -1 was measured using a capillary of 1 mm ⁇ ⁇ 20 mmL as a capillary using a Capillograph manufactured by Toyo Seiki Seisaku-sho, Ltd.
  • Olefin-based copolymer / Olefin-based copolymer 1 Bondfast 7L (ethylene-glycidyldimethacrylate-methyl acrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd., GMA: 3% by mass, MA: 27) mass%)
  • Olefin-based copolymer 2 Bondfast 7M (manufactured by Sumitomo Chemical Co., Ltd.) (ethylene-glycidyl dimethacrylate-methyl acrylate copolymer, GMA: 6% by mass, MA: 27% by mass)
  • Bondfast 2C ethylene-glycidyl dimethacrylate copolymer, GMA: 6% by mass manufactured by Sumitomo Chemical Co., Ltd.
  • -Olefin copolymer 4 Bond First E (ethylene-glycidyl dimethacrylate copolymer, GMA: 12% by mass) manufactured by Sumitomo Chemical Co., Ltd.
  • -Olefin copolymer 5 Lexpearl RA3150 (ethylene-glycidyl dimethacrylate copolymer, GMA: 15% by mass) manufactured by Japan Polyolefin Co., Ltd.
  • GMA xyl dimethacrylate copolymer
  • Tables 1 and 2 the content ratio of the structural unit derived from the glycidyl ester of an ⁇ , ⁇ -unsaturated acid is shown as “GMA: xx% by mass”.
  • Silane coupling agent / alkoxysilane compound KBE-903P manufactured by Shin-Etsu Chemical Co., Ltd.
  • Fluidity A rod-shaped molded product having a width of 20 mm and a thickness of 1 mm (a side gate having a width of 12 mm and a thickness of 6 mm) was molded by injection molding using the above pellets, and the flow length was measured.
  • the conditions for injection molding are as follows. Cylinder temperature: 320 ° C Injection pressure: 100MPa Holding pressure: 100MPa Mold temperature: 150 ° C, Mold: Spiral flow mold with one point gate Next, the average value of five tests was taken as the flow length. As described above, when the flow length is 110 mm to 300 mm, it is possible to mold a thin resin portion in a complicated structure without excessively increasing the molding temperature. Tables 1 and 2 show the evaluation results.
  • FIG. 1 is a view showing a test piece 1 formed by insert molding
  • FIG. 2 is a view showing an insert member 11
  • FIG. 3 is a view showing dimensions of the test piece 1.
  • the test piece 1 is formed 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 by using the pellets obtained as described above. As shown in FIG.
  • the insert member 11 has a columnar shape, and the upper and lower surfaces thereof have an arc shape on one side and an acute angle shape on the other side, and have a tear shape.
  • the acute angle portion has an arc-shaped tip and a radius of curvature r of 0.2 mm.
  • the insert member 11 is higher than the height of the cylindrical resin member 10 and a part thereof protrudes (see FIG. 1A).
  • the center O 1 of the circle of which the arc of the insert member 11 is part does not coincide with the center O 2 of the circle of the resin member 10, and the acute angle The side is arranged so as to approach the side surface of the resin member 10.
  • 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 is a thin weld portion (thin portion). ).
  • FIG. 3 shows the dimensions of the test piece, and the unit is mm.
  • the test piece was treated at 121 ° C., 2 atm, and 100% RH for 500 hours using a pressure cooker test (PCT) apparatus.
  • PCT pressure cooker test
  • a cycle of cooling at -40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours was repeated on the treated test piece using a thermal shock tester (manufactured by Espec Corporation).
  • the weld was observed every 20 cycles.
  • the number of cycles when a crack occurred in the weld was evaluated as an index of heat shock resistance. Tables 1 and 2 show the evaluation results. When the number of cycles is 140 or more, the heat shock resistance is excellent, and when it is 150 or more, the heat shock resistance is particularly excellent. When it is 175 or more, the heat shock resistance is remarkably excellent.
  • Table 1 shows that all of Examples 1 to 12 were excellent in fluidity and heat shock resistance after PCT. That is, it is understood that the PAS resin compositions of Examples 1 to 12 have LLC resistance and high fluidity. On the other hand, from Table 2, in Comparative Examples 1 to 9, all of the evaluations could not be made good at the same time. For example, Comparative Example 1 was inferior in LLC resistance because the melt viscosity of the PAS resin was low. Comparative Example 2 was inferior in LLC resistance because of a small amount of glass fibers, and Comparative Example 3 was inferior in LLC resistance because of a large amount of glass fibers.
  • Comparative Example 4 containing no olefin-based copolymer was inferior in LLC resistance
  • Comparative Example 5 containing a large amount of olefin-based copolymer was inferior in fluidity.
  • Comparative Examples 6 and 9 in which the content ratio of the constituent unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid in the olefin-based copolymer was large were all inferior in fluidity.
  • Comparative Examples 7 and 8, which did not contain a silane coupling agent were all inferior in LLC resistance.
  • the melt viscosity of the PAS resin, the predetermined olefin-based copolymer and its content, the glass fiber and its content It can be seen that both the amount, the silane coupling agent and its content need to be within the ranges specified in the present embodiment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de poly(sulfure d'arylène) utilisée pour mouler un article moulé qui peut entrer en contact avec des fluides, notamment de l'eau, la composition contenant 2,0-9,0 parties en masse d'un copolymère oléfinique prescrit, 5-40 parties en masse de fibres de verre et 0,1-0,7 partie en masse d'un agent de couplage de type silane pour 100 parties en masse d'une résine de poly(sulfure d'arylène) présentant une viscosité à l'état fondu de 100-250 Pa·s ; le rapport des teneurs en motifs structuraux dérivés d'esters glycidyliques d'acide α,β-insaturé et en copolymère oléfinique étant de 1,0-8,0 % en masse ; et la composition présentant une longueur d'écoulement à 20 mm de largeur et à 1 mm d'épaisseur de 110 à 300 mm à une température de cylindre, une pression d'injection, une pression de pause de fermeture de moule et une température de moule prescrites.
PCT/JP2019/035732 2018-09-14 2019-09-11 Composition de résine de poly(sulfure d'arylène), article moulé et article moulé par insertion WO2020054772A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-172512 2018-09-14
JP2018172512 2018-09-14

Publications (1)

Publication Number Publication Date
WO2020054772A1 true WO2020054772A1 (fr) 2020-03-19

Family

ID=69776830

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/035732 WO2020054772A1 (fr) 2018-09-14 2019-09-11 Composition de résine de poly(sulfure d'arylène), article moulé et article moulé par insertion

Country Status (1)

Country Link
WO (1) WO2020054772A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022080129A1 (fr) * 2020-10-16 2022-04-21
WO2023017762A1 (fr) * 2021-08-11 2023-02-16 東ソー株式会社 Complexe élément métallique-élément de sulfure de polyarylène et son procédé de production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003716A (ja) * 2000-06-16 2002-01-09 Toray Ind Inc ポリフェニレンスルフィド樹脂組成物及び射出成形品
JP2011256387A (ja) * 2010-06-11 2011-12-22 Ticona Llc ブロー成形品およびその製造方法
JP2014502690A (ja) * 2010-12-22 2014-02-03 ティコナ・エルエルシー 複雑な３次元構成を有する高温導管
CN106147230A (zh) * 2015-04-09 2016-11-23 东丽先端材料研究开发（中国）有限公司 高流动性高刚性的聚苯硫醚树脂组合物及其成型品
WO2019026869A1 (fr) * 2017-08-02 2019-02-07 ポリプラスチックス株式会社 Composition de résine polysulfure d'arylène et corps en contact avec un carburant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003716A (ja) * 2000-06-16 2002-01-09 Toray Ind Inc ポリフェニレンスルフィド樹脂組成物及び射出成形品
JP2011256387A (ja) * 2010-06-11 2011-12-22 Ticona Llc ブロー成形品およびその製造方法
JP2014502690A (ja) * 2010-12-22 2014-02-03 ティコナ・エルエルシー 複雑な３次元構成を有する高温導管
CN106147230A (zh) * 2015-04-09 2016-11-23 东丽先端材料研究开发（中国）有限公司 高流动性高刚性的聚苯硫醚树脂组合物及其成型品
WO2019026869A1 (fr) * 2017-08-02 2019-02-07 ポリプラスチックス株式会社 Composition de résine polysulfure d'arylène et corps en contact avec un carburant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022080129A1 (fr) * 2020-10-16 2022-04-21
WO2022080129A1 (fr) * 2020-10-16 2022-04-21 ポリプラスチックス株式会社 Composant de système de refroidissement pour véhicules, ledit composant pouvant entrer en contact avec un fluide contenant de l'eau
WO2023017762A1 (fr) * 2021-08-11 2023-02-16 東ソー株式会社 Complexe élément métallique-élément de sulfure de polyarylène et son procédé de production

Similar Documents

Publication Publication Date Title
JP5618025B2 (ja) ポリアリーレンスルフィド樹脂組成物および成形体
JP2009030030A (ja) ポリフェニレンスルフィド樹脂組成物およびそれからなる成形品
JP2008075049A (ja) ポリフェニレンスルフィド樹脂組成物および成形品
JP5510624B2 (ja) ポリアリーレンスルフィド樹脂組成物および成形体
KR102647580B1 (ko) 금속 수지 복합체 및 그 제조 방법
KR102141928B1 (ko) 폴리아릴렌설피드 수지 조성물, 성형품 및 제조 방법
JP6809083B2 (ja) ポリアリーレンスルフィド樹脂組成物、成形品およびそれらの製造方法
WO2020054772A1 (fr) Composition de résine de poly(sulfure d'arylène), article moulé et article moulé par insertion
WO2019208709A1 (fr) Composition de résine sulfure de polyarylène et article de moulage sur prisonnier
JP2020109135A (ja) 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
JPWO2019208377A1 (ja) ポリアリーレンスルフィド樹脂組成物、成形品、複合成形品及びそれらの製造方法
JP2020084027A (ja) ポリアリーレンスルフィド樹脂組成物及びその製造方法
JP2005060454A (ja) ポリフェニレンスルフィド樹脂組成物および複合成形体
JP2007246883A (ja) ポリフェニレンスルフィド樹脂組成物およびその成形体
JP6797360B2 (ja) ポリアリーレンスルフィド樹脂組成物、成形品及び製造方法
JP7136381B1 (ja) ポリアリーレンスルフィド樹脂組成物、ポリアリーレンスルフィド樹脂組成物の製造方法、成形品、成形品の製造方法
JP6823841B2 (ja) 金属樹脂複合体及びその製造方法
WO2021246268A1 (fr) Composition de résine de sulfure de polyarylène, article moulé, et procédés de fabrication associés
JP2021075640A (ja) 水を含む流体と接触し得る車両用冷却系部品
JP6753470B2 (ja) ポリアリーレンスルフィド樹脂組成物、成形品及び製造方法
JP2007211116A (ja) 射出成形キャニスター。
JP7311051B2 (ja) ポリアリーレンスルフィド樹脂組成物、成形品及びそれらの製造方法
JP7136394B1 (ja) ポリアリーレンスルフィド樹脂組成物、成形品およびそれらの製造方法
JP6769582B2 (ja) ポリアリーレンスルフィド樹脂組成物、成形品、複合成形品及びそれらの製造方法
JP2017088878A (ja) ポリアリーレンスルフィド樹脂組成物および成形品

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: 19859577

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: 19859577

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP