WO2022215395A1 - Composition de résine de sulfure de polyarylène, article moulé, et procédés de production de ladite composition de résine de sulfure de polyarylène et dudit article moulé - Google Patents

Composition de résine de sulfure de polyarylène, article moulé, et procédés de production de ladite composition de résine de sulfure de polyarylène et dudit article moulé Download PDF

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Publication number
WO2022215395A1
WO2022215395A1 PCT/JP2022/009016 JP2022009016W WO2022215395A1 WO 2022215395 A1 WO2022215395 A1 WO 2022215395A1 JP 2022009016 W JP2022009016 W JP 2022009016W WO 2022215395 A1 WO2022215395 A1 WO 2022215395A1
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Prior art keywords
parts
resin composition
polyarylene sulfide
sulfide resin
mass
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PCT/JP2022/009016
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English (en)
Japanese (ja)
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啓介 山田
由希 出口
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Dic株式会社
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Priority to JP2022533167A priority Critical patent/JP7136394B1/ja
Publication of WO2022215395A1 publication Critical patent/WO2022215395A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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 resin composition, a polyarylene sulfide resin molded article, and a method for producing them.
  • PAS polyarylene sulfide
  • PPS polyphenylene sulfide
  • Automotive fuel system parts are exposed to fuel such as gasoline and their vapors in addition to high temperature environments. However, there was a problem that the physical strength was lowered.
  • Patent Document 1 a resin composition obtained by blending a PPS resin having a non-Newton index of 1.15 or more, a fibrous filler and a non-fibrous filler in a specific range of ratio
  • Patent Document 2 a resin composition containing a PPS resin having a peak molecular weight in the molecular weight distribution of 34,200 to 100,000 and a thermoplastic elastomer comprising an acid-modified ⁇ -olefin copolymer and an epoxy resin is provided (Patent Document 2). reference).
  • JP 2008-266616 A Japanese Patent Application Laid-Open No. 2004-300272 JP-A-2006-45401
  • the problem to be solved by the present invention is to provide a polyarylene sulfide molded article that suppresses swelling due to fuel and has excellent dimensional stability and mechanical properties even after immersion in fuel, a PAS resin composition that can provide the molded article, and It is to provide those manufacturing methods.
  • the present inventors have made intensive studies to solve the above problems.
  • the inventors have found that the molded article has excellent fuel swelling resistance and excellent dimensional stability and mechanical properties after being immersed in fuel, leading to the completion of the present invention.
  • the PAS resin composition for fuel system parts of the present disclosure is A PAS resin composition for fuel system parts, comprising a PAS resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components,
  • the PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
  • the glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). .
  • the total amount of the glass fiber (B) and the non-fibrous filler (C) is 180 to 300 mass parts with respect to 100 mass parts of the PAS resin (A). It is preferably in the range of part. In this case, the fuel swelling resistance effect can be achieved at a higher level.
  • the molded article of the present disclosure is obtained by melt-molding the PAS resin composition for fuel system parts described above.
  • the method for producing the PAS resin composition for fuel system parts of the present disclosure comprises: A fuel comprising a step of blending a PAS resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components, and melt-kneading them in a temperature range above the melting point of the PAS resin (A).
  • a method for producing a PAS resin composition for system parts comprising:
  • the PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
  • the glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). .
  • the total amount of the glass fiber (B) and the non-fibrous filler (C) is 180 parts per 100 parts by mass of the PAS resin (A). It is preferably in the range of up to 300 parts by mass. In this case, fuel swelling resistance can be further improved.
  • the method for producing a molded article of the present disclosure includes a step of melt-molding the PAS resin composition obtained by the method of producing a PAS resin composition for fuel system parts of the present disclosure, and a step of annealing the resulting molded article. have.
  • fuel swelling resistance, dimensional stability, and mechanical strength can be further improved.
  • a molded article containing a PAS resin, a fibrous filler, and a non-fibrous filler having excellent dimensional stability and mechanical properties, and excellent fuel swelling resistance, and the molded article It is possible to provide a PAS resin composition that can provide and a method for producing them.
  • the PAS resin composition of the present disclosure is a PAS resin composition for fuel system parts, which is obtained by blending PAS resin (A), glass fiber (B), and non-fibrous filler (C) as essential components.
  • the PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
  • the glass fiber (B) is 50 to 150 parts by mass and the non-fibrous filler (C) is 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). This will be explained below.
  • PAS resin (A)> The PAS resin composition of the present disclosure contains a crosslinked PAS resin as an essential component.
  • a PAS resin has a resin structure in which a repeating unit is a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the following general formula (1)
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). and, if necessary, the following general formula (2)
  • the trifunctional structural site represented by formula (2) is preferably in the range of 0.001 to 3 mol%, particularly in the range of 0.01 to 1 mol%, relative to the total number of moles with other structural sites. is preferably
  • the structural moiety represented by the general formula (1), particularly R 1 and R 2 in the formula is preferably a hydrogen atom from the viewpoint of the mechanical strength of the PAS resin.
  • examples include those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4).
  • the structure in which the sulfur atom is bonded to the aromatic ring in the repeating unit at the para position represented by the general formula (3) is particularly desirable in terms of heat resistance and crystallinity of the PAS resin. preferable.
  • the PAS resin has not only the structural sites represented by the general formulas (1) and (2), but also the following structural formulas (5) to (8)
  • the structural sites represented by the general formulas (5) to (8) are 10 mol % or less from the viewpoint of heat resistance and mechanical strength of the PAS resin.
  • the binding mode thereof may be either a random copolymer or a block copolymer.
  • the PAS resin may have a naphthyl sulfide bond or the like in its molecular structure. The following are preferable.
  • a low-molecular-weight linear polymer obtained by condensation polymerization of a monomer mainly composed of a bifunctional halogen aromatic compound represented by the general formula (1) is treated with oxygen or an oxidizing agent.
  • a method of increasing the melt viscosity by heating at a high temperature in the presence of a compound having 3 or more halogen functional groups as represented by the above general formula (2) can also be used when polycondensing.
  • a method of partially forming a branched or crosslinked structure by using a small amount of a monomer such as a polyhaloaromatic compound can also be used.
  • the physical properties of the PAS resin are not particularly limited as long as they do not impair the effects of the present invention, but are as follows.
  • melt viscosity The melt viscosity of the PAS resin used in the present disclosure is not particularly limited, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 Pa s or more because the balance between fluidity and mechanical strength is good. and is preferably in the range of 1000 Pa ⁇ s or less, more preferably in the range of 500 Pa ⁇ s or less, and still more preferably in the range of 200 Pa ⁇ s or less.
  • the isothermal crystallization time of the PAS resin used in the present disclosure is preferably in the range of 0.7 minutes or more, more preferably 0.9 minutes or more, because moldability, mechanical strength, and fuel swelling resistance are improved. and preferably in the range of 3.7 minutes or less, more preferably in the range of 3.0 minutes or less, and even more preferably in the range of 2.2 minutes or less. Within this range, the PAS resin exhibits excellent crystallization properties, and exhibits good moldability, mechanical strength, and fuel swelling resistance.
  • the isothermal crystallization time was measured using a differential scanning calorimeter. After melting the PAS resin at 350°C for 3 minutes, it was rapidly cooled to 240°C at a rate of 150°C/min. The measured value is the time required to reach the top of the exothermic peak during quenching.
  • the differential scanning calorimeter includes, for example, a DSC device Pyris Diamond manufactured by Perkin Elmer.
  • non-Newton exponent is the shear rate (SR ) and shear stress (SS) are measured and calculated using the following formula. The closer the non-Newtonian index (N value) to 1, the more linear the structure, and the higher the non-Newtonian index (N value), the more branched the structure.
  • the PAS resin used in the present disclosure preferably has a sodium atom content of 1800 ppm or less, more preferably 1600 ppm or less, derived from the sulfidation agent used as the starting material.
  • the lower limit of the sodium concentration is preferably reduced to below the detection limit, but excessive reduction may reduce productivity, so it is preferably in the range of 40 ppm or more, and further in the range of 50 ppm or more. is more preferable, and a range of 70 ppm or more is particularly preferable.
  • the sodium atom content contained in the PAS resin was determined by baking the resin at 500° C. and then baking the resin at 530° C. for 6 hours. (manufactured by Shimadzu Corporation) to refer to the concentration of sodium atoms (mass standard).
  • the method for producing the PAS resin is not particularly limited, but for example (production method 1), a dihalogeno aromatic compound is added in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymer components are added to polymerize.
  • (Manufacturing method 2) A method of polymerizing a dihalogeno aromatic compound in the presence of a sulfidating agent or the like in a polar solvent, and if necessary, adding a polyhalogeno aromatic compound or other copolymerization components, (Manufacturing method 3) A method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary, (Manufacturing method 4) A diiodo aromatic compound and elemental sulfur are combined with a functional group such as a carboxy group or an amino group. A method of performing melt polymerization under reduced pressure in the presence of an optional polymerization inhibitor, and the like.
  • the method of (manufacturing method 2) is versatile and preferable.
  • an alkali metal salt of carboxylic acid or sulfonic acid, or an alkali hydroxide may be added in order to adjust the degree of polymerization.
  • a hydrous sulfidation agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at such a rate that water can be removed from the reaction mixture, and dihalogeno is produced in the organic polar solvent.
  • a method for producing a PAS resin by controlling the range of (see JP-A-07-228699), and a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, if necessary
  • a polyhalogeno aromatic compound or other copolymer components are added, and an alkali metal hydrosulfide and an organic acid alkali metal salt are added in an amount of 0.01 to 0.9 mol per 1 mol of the sulfur source.
  • dihalogenoaromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4′-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p '-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalo
  • the post-treatment method of the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited. is added, the solvent is distilled off under reduced pressure or normal pressure, and the solid matter after the solvent is distilled off is treated with water, a reaction solvent (or an organic solvent having an equivalent solubility for the low-molecular-weight polymer), acetone, methyl ethyl ketone. , a method of washing with a solvent such as alcohols once or twice or more, followed by neutralization, washing with water, filtration and drying; , ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and are poor solvents for at least PAS) as precipitants.
  • a solvent such as alcohols once or twice or more
  • a reaction solvent or low-molecular-weight
  • An organic solvent having the same solubility as the polymer is added and stirred, filtered to remove the low molecular weight polymer, and then washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc.
  • Post-treatment 4 After completion of the polymerization reaction, add water to the reaction mixture, wash with water, filter, and if necessary, add an acid or base at the time of washing with water.
  • the reaction mixture is filtered, and if necessary, washed with a reaction solvent once or twice or more, and further washed with water, filtered and dried. , etc.
  • the reactivity, crystallization rate, sodium content, etc. of the PAS resin can be controlled by adding an acid or base during the water washing step to adjust the pH.
  • the pH after the step can be controlled to be in the range of 6.5-11.5, more preferably in the range of 6.5-8.5.
  • the PAS resin may be dried in a vacuum, or in the air or in an inert gas atmosphere such as nitrogen. You can do it with
  • the method for cross-linking the linear-structured PAS resin thus obtained is not particularly limited as long as it is a known method.
  • a method of performing heat treatment in a toxic atmosphere can be mentioned.
  • the heating conditions are preferably in the range of 180° C. or higher to 20° C. lower than the melting point of the PAS resin, from the viewpoint of the time required for the heat treatment and the thermal stability of the PAS resin when it is melted after the heat treatment.
  • the melting point here refers to the one measured according to JIS K 7121 using a differential scanning calorimeter (for example, Perkin Elmer DSC device Pyris Diamond).
  • the oxygen concentration is preferably 5% by volume or more, more preferably 10% by mass or more, from the viewpoint of a high oxidation rate and a short processing time. and from the viewpoint of suppressing the increase in radical generation amount and suppressing the thickening during heat treatment, and from the viewpoint of good hue, preferably 30% by volume or less, more preferably 25% by volume or less. It can be within the range.
  • the PAS resin composition of the present disclosure contains glass fiber (B) as an essential component.
  • the raw material of the glass fiber (B) used in the present disclosure those known to those skilled in the art can be used, and the fiber diameter, fiber length, aspect ratio, etc. can be appropriately adjusted according to the use of the molded product. .
  • the glass fiber (B) used in the present disclosure may be processed with a surface treatment agent or a sizing agent.
  • a surface treatment agent or a sizing agent examples include silane compounds, titanate compounds, acrylic resins, urethane resins, polyether resins and epoxy resins having functional groups such as amino groups, epoxy groups, isocyanate groups and vinyl groups.
  • At least one polymer selected from the group may be mentioned, and it is particularly preferable to contain a urethane resin from the viewpoint of suppressing excessive fibrillation during processing.
  • the surface treatment agent or sizing agent contains a urethane resin
  • the content is not particularly limited, but from the viewpoint of fuel swelling resistance, it is preferably in the range of 35% by mass or less, and in the range of 20% by mass or less. is more preferable.
  • the blending amount of the glass fiber (B) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and 70 parts by mass with respect to 100 parts by mass of the PAS resin (A).
  • a range of at least 1 part is more preferable.
  • it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 85 parts by mass or less, from the viewpoint of fluidity and workability of the resin composition.
  • Non-fibrous filler (C) contains a non-fibrous filler (C) as an essential component.
  • the non-fibrous filler (C) used in the present disclosure is an essential component that improves fuel swelling resistance and high dimensional accuracy.
  • the non-fibrous filler (C) known and commonly used materials can be used, and examples thereof include fillers of various shapes such as plate-like ones and powder-like ones.
  • the range of the average particle size (D 50 ) of the non-fibrous filler (C) used in the present disclosure is not particularly limited, but from the viewpoint of excellent mechanical strength and fluidity, it is preferably in the range of 20 ⁇ m or less. , 15 ⁇ m or less, more preferably 8 ⁇ m or less, and particularly preferably 2 ⁇ m or less.
  • the average particle size is an average particle size (D 50 ) obtained based on the particle size distribution measured according to a conventional method using a laser diffraction/scattering particle size distribution analyzer (Microtrac MT3300EXII).
  • the amount of the non-fibrous filler (C) blended in the PAS resin composition of the present disclosure is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 50 parts by mass with respect to 100 parts by mass of the PAS resin (A). parts or more, more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 85 parts by mass or less.
  • the resin composition has good fuel swelling resistance and good moldability, especially mold releasability, and the molded product exhibits high dimensional accuracy, which is preferable.
  • the total amount of the glass fiber (B) and the non-fibrous filler (C) is preferably in the range of 180 parts by mass or more with respect to 100 parts by mass of the PAS resin (A). , 200 parts by weight or more. Also, it is preferably in the range of 300 parts by mass or less, more preferably in the range of 250 parts by mass or less. This range is preferable because the resin composition has good fuel swelling resistance and workability, and is excellent in mechanical strength.
  • the PAS resin composition of the present disclosure can optionally contain a silane coupling agent as an optional component.
  • the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably a silane coupling agent having a functional group that reacts with a carboxy group, such as an epoxy group, an isocyanato group, an amino group or a hydroxyl group. mentioned.
  • Examples of such silane coupling agents include epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.
  • the silane coupling agent is not an essential component, but when blended, the amount is not particularly limited as long as the effect of the present invention is not impaired. , preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less. This range is preferable because the resin composition has good moldability, particularly releasability, and the mechanical strength of the molded product is improved.
  • the PAS resin composition of the present disclosure can optionally contain a thermoplastic elastomer as an optional component.
  • thermoplastic elastomers include polyolefin elastomers, fluorine elastomers, and silicone elastomers, among which polyolefin elastomers are preferred.
  • the blending amount is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.01 parts by mass or more, more preferably The range is from 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. This range is preferable because the resulting PAS resin composition has improved impact resistance.
  • the polyolefin elastomer is an ⁇ -olefin homopolymer, a copolymer of two or more ⁇ -olefins, or a copolymer of one or two or more ⁇ -olefins and a vinyl polymerizable compound having a functional group. coalescence is mentioned.
  • examples of the ⁇ -olefin include ⁇ -olefins having from 2 to 8 carbon atoms such as ethylene, propylene and 1-butene.
  • Examples of the vinyl polymerizable compound having the functional group include vinyl acetate; ⁇ , ⁇ -unsaturated carboxylic acids such as (meth)acrylic acid; ⁇ , ⁇ - Alkyl esters of unsaturated carboxylic acids; Metal salts of ⁇ , ⁇ -unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, zinc, etc.); glycidyl esters of ⁇ -unsaturated carboxylic acids; ⁇ , ⁇ -unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; derivatives of the above ⁇ , ⁇ -unsaturated dicarboxylic acids (monoesters, diesters, acid anhydrides ), etc., or two or more.
  • the above thermoplastic elastomers may be used alone or in combination of two or more.
  • the PAS resin composition of the present disclosure may contain polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, Polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoride ethylene resin, polystyrene resin, ABS resin, phenolic resin, urethane Synthetic resins such as resins and liquid crystal polymers (hereinafter simply referred to as synthetic resins) can be blended as optional components.
  • synthetic resins such as resins and liquid crystal polymers
  • the synthetic resin is not an essential component, but when blended, the blending ratio is not particularly limited as long as it does not impair the effects of the present invention.
  • the ratio of the synthetic resin to be blended in the resin composition according to the present disclosure is, for example, a range of 5 parts by mass or more to 100 parts by mass of the PAS resin (A), and a range of 15 parts by mass or less.
  • the degree of In other words, the ratio of the PAS resin to the total of the PAS resin (A) and the synthetic resin is preferably in the range of (100/115) or more, and more preferably in the range of (100/105) or more. Range.
  • the PAS resin composition of the present disclosure also contains a coloring agent, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, an auxiliary flame retardant, and an antirust agent.
  • a coloring agent an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, an auxiliary flame retardant, and an antirust agent.
  • And release agents metal salts and esters of fatty acids with 18 to 30 carbon atoms including stearic acid and montanic acid, polyolefin waxes such as polyethylene, etc. May be blended.
  • additives are not essential components, for example, with respect to 100 parts by mass of the PAS resin (A), preferably in the range of 0.01 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass It may be used in an amount of not more than 10 parts by mass, more preferably not more than 10 parts by mass, and adjusted appropriately according to the purpose and application so as not to impair the effects of the present invention.
  • the PAS resin (A), the glass fiber (B), and the non-fibrous filler (C) are blended as essential components, and the melting point of the PAS resin (A) or higher is wherein the PAS resin (A) is a crosslinked PAS resin and the isothermal crystallization time is 0.7 50 to 150 parts by mass of the glass fiber (B) and 50 to 150 parts by mass of the non-fibrous filler (C) with respect to 100 parts by mass of the PAS resin (A). It is characterized by being in the range of part. Details will be described below.
  • the manufacturing method of the PAS resin composition of the present disclosure has a step of blending the essential components and melt-kneading them in a temperature range equal to or higher than the melting point of the PAS resin (A). More specifically, the PAS resin composition of the present disclosure contains each essential component and, if necessary, other optional components.
  • the method for producing the resin composition used in the present disclosure is not particularly limited, but a method of blending essential components and optionally optional components and melt-kneading, more specifically, a tumbler or Henschel as necessary A method of homogeneously dry-mixing with a mixer or the like, then introducing into a twin-screw extruder and melt-kneading may be mentioned.
  • Melt-kneading is performed in a temperature range in which the resin temperature is the melting point of the PAS resin (A) or higher, preferably in a temperature range in which the melting point is +10°C or higher, more preferably the melting point is +10°C or higher, and further preferably the melting point is +20°C or higher. , preferably the melting point + 100°C or less, more preferably the melting point + 50°C or less.
  • melt-kneader a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. It is preferable to melt-knead while appropriately adjusting the range of and melt-kneading under conditions where the ratio (discharge rate / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). is more preferred. Moreover, addition and mixing of each component to the melt-kneader may be performed simultaneously, or may be performed separately.
  • the glass fiber (B) which is an essential component among the above components
  • the ratio of the distance from the extruder resin input part (top feeder) to the side feeder with respect to the total screw length of the twin-screw kneading extruder is preferably 0.1 or more, and 0 .3 or more is more preferable. Also, the ratio is preferably 0.9 or less, more preferably 0.7 or less.
  • the PAS resin composition according to the present disclosure obtained by melt-kneading in this way is a molten mixture containing the essential components, optional components added as necessary, and components derived from them. Therefore, the PAS resin composition of the present disclosure has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed.
  • the PAS resin composition according to the present disclosure is processed into pellets, chips, granules, powder, and the like by a known method, for example, extruding the resin composition in a molten state into strands. Therefore, it is preferable to pre-dry in the temperature range of 100 to 150° C. as necessary.
  • the molded article of the present disclosure is obtained by melt-molding a PAS resin composition. Further, the method for producing a molded article of the present disclosure has a step of melt-molding the PAS resin composition. Therefore, the molded article of the present disclosure has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. When the PAS resin composition has such a morphology, a molded article having excellent fuel swelling resistance and mechanical strength can be obtained.
  • the PAS resin composition of the present disclosure can be subjected to various molding such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, transfer molding. Also suitable for injection molding applications.
  • various molding conditions are not particularly limited, and molding can be performed by a general method.
  • the resin temperature is in the range of the melting point of the PAS resin (A) or higher, preferably the melting point +10°C or higher, more preferably the melting point +10°C to the melting point +100°C, more preferably
  • the composition may be molded by injecting it into a mold through the resin discharge port.
  • the mold temperature may also be set within a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.
  • the method of manufacturing a PAS resin molded product of the present disclosure has a step of annealing the molded product.
  • Optimum conditions for the annealing treatment are selected according to the use, shape, etc. of the molded product, and the annealing temperature is preferably in the range of 100° C. or higher, more preferably in the range of 120° C. or higher. On the other hand, it is preferably in the range of 260° C. or lower, more preferably in the range of 240° C. or lower.
  • the annealing time is not particularly limited, it is preferably in the range of 0.5 hours or longer, and more preferably in the range of 1 hour or longer.
  • the range of 10 hours or less is preferably in the range of 10 hours or less, more preferably in the range of 8 hours or less. This range is preferable because the distortion of the resulting molded product is reduced and the crystallinity of the resin is improved.
  • Annealing may be performed in the air, but is preferably performed in an inert gas such as nitrogen gas.
  • the PAS resin molded product of the present disclosure has a weight change rate per unit amount when immersed in FAMB (mixed solution of 30 vol% isooctane + 50 vol% toluene + 5 vol% ethanol + 15 vol% diisobutylene) at 80 ° C. for 1500 hours. , 1.3% or less. Within this range, excellent dimensional stability and mechanical strength can be maintained even after immersion in fuel.
  • FAMB mixed solution of 30 vol% isooctane + 50 vol% toluene + 5 vol% ethanol + 15 vol% diisobutylene
  • the PAS resin molded article of the present disclosure is characterized by being excellent in fuel swelling resistance.
  • Fossil fuels such as heavy oil, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane, unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, cyclohexane , cyclic saturated hydrocarbons such as cycloheptane, cyclooctane, cyclodecane and decalin; cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene; It may be one or a plurality of hydrocarbons represented by aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Fuel system parts include, for example, pipes, containers, joints, etc. More specifically, in-vehicle fuel system parts such as fuel tanks, fuel tubes, fuel sensors, fuel pumps, vane pumps, auto ratio flow meters, etc. It can be used preferably.
  • the molded article of the present disclosure is not only for fuel system parts for vehicles, but also printing parts such as containers, nozzles, brushes, cartridges, pumps, etc. It can also be suitably used for cleaning equipment parts, sliding parts that come into contact with lubricating oil, and cleaning equipment parts that use hydrocarbons as solvents. In addition to this, it can also be made into the following normal resin moldings.
  • protection and support members for box-shaped electrical and electronic component integrated modules Multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, Oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, Electric/electronic parts such as parabolic antennas, computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio/laser discs/compact discs/DVD discs/Blu-ray discs Household and office electrical equipment such as audio/visual equipment parts such as discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and plumbing equipment parts such as water heaters, bath water volume, temperature sensors, etc.
  • Machine-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc.: microscopes, binoculars, cameras, watches
  • precision machinery related parts such as; alternator terminal, alternator connector, brush holder, slip ring, IC regulator, potentiometer base for light dimmer, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel related ⁇ Exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank Shaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, dust distributors, Starter switch, ignition coil and its
  • Examples 1 and 2 and Comparative Examples 1 to 3 Each material was blended according to the compositional components and blending amounts shown in Table 1. After that, these compounding materials are put into a vented twin-screw extruder “TEX-30 ⁇ (product name)” manufactured by The Japan Steel Works, Ltd., and the resin component discharge amount is 30 kg / hr, the screw rotation speed is 200 rpm, and the set resin temperature is 320 ° C. The pellets of the resin composition were obtained by melt-kneading. The glass fiber was fed from the side feeder (S/T ratio 0.5), and the other materials were premixed uniformly in a tumbler and fed from the top feeder. After drying the obtained pellets of the resin composition in a gear oven at 140° C. for 2 hours, they were injection molded to prepare various test pieces, and the following tests were performed.
  • TEX-30 ⁇ product name
  • CM15 is a mixed solution of 15 vol% methanol + 85 vol% Fuel C
  • FAMB is a mixed solution of 30 vol% isooctane + 50 vol% toluene + 5 vol% ethanol + 15 vol% diisobutylene
  • Fuel C is 50 vol% isooctane + It is a mixed solution of 50 vol % toluene.
  • test piece and fuel prepared in the same manner as in (1) are sealed in an autoclave, heated to 80 ° C., and the autoclave is filled with fuel vapor. It was left exposed for 1500 hours. After slowly cooling to room temperature, the dimension of the test piece in the direction perpendicular to the resin flow direction was measured, and the dimensional change rate relative to the test piece not exposed to fuel vapor was calculated.
  • PAS resin crosslinked PPS resin A-1 melt viscosity (V6) 42 Pa s, sodium content 1200 ppm, isothermal crystallization time 1.1 minutes
  • a-2 melt viscosity (V6) 44 Pa s, sodium content 1400 ppm , Isothermal crystallization time 4.0 minutes
  • Linear polyphenylene sulfide resin a-3 Melt viscosity (V6) 42 Pa s, sodium content 310 ppm, isothermal crystallization time 5.0 minutes
  • ⁇ Glass fiber B-1 surface-treated glass fiber
  • sizing agent chopped strand containing 8% urethane resin, 11% polyether resin, 81% other components, fiber diameter 10 ⁇ m, fiber length 3 mm
  • Non-fibrous filler C-1 calcium carbonate, particle size (D 50 ) 1.7 ⁇ m
  • C-2 Talc, particle size (D 50 ) 14 ⁇ m

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  • 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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : un article moulé en résine de sulfure de polyarylène (PAS) qui comprend une résine PAS, une charge fibreuse et une charge non fibreuse, supprime le gonflement provoqué par le carburant, et présente une excellente stabilité dimensionnelle et des propriétés mécaniques même après avoir été immergé dans un carburant ; une composition de résine PAS qui peut fournir ledit article moulé en résine PAS ; et des procédés de production associés. Plus spécifiquement, l'invention concerne : une composition de résine PAS pour des composants de système de carburant, qui contient une résine PAS (A), des fibres de verre (B), et une charge non fibreuse (C) en tant que composants essentiels, la composition de résine PAS étant caractérisée en ce que la résine PAS (A) est une résine PAS réticulée, a un temps de cristallisation isotherme de 0,7 à 3,7 minutes, et les fibres de verre (B) sont contenues en une quantité de 50 à 150 parties en masse et la charge non fibreuse (C) en une quantité de 50 à 150 parties en masse, par rapport à 100 parties en masse de la résine PAS (A) ; un article moulé ; et des procédés respectivement pour la production de la composition de résine PAS et de l'article moulé.
PCT/JP2022/009016 2021-04-08 2022-03-03 Composition de résine de sulfure de polyarylène, article moulé, et procédés de production de ladite composition de résine de sulfure de polyarylène et dudit article moulé WO2022215395A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62230850A (ja) * 1986-03-08 1987-10-09 バイエル・アクチエンゲゼルシヤフト 急速結晶化ポリフエニレンスルフイド組成物
US5340861A (en) * 1993-05-03 1994-08-23 Industrial Technology Research Institute Polyphenylene sulfide composition with improved crystallizing characteristic
WO2020171164A1 (fr) * 2019-02-22 2020-08-27 Dic株式会社 Composition à base de résine de poly(sulfure d'arylène), corps moulé de celle-ci, procédé de production d'une composition à base de résine de poly(sulfure d'arylène) et procédé de production d'un corps moulé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62230850A (ja) * 1986-03-08 1987-10-09 バイエル・アクチエンゲゼルシヤフト 急速結晶化ポリフエニレンスルフイド組成物
US5340861A (en) * 1993-05-03 1994-08-23 Industrial Technology Research Institute Polyphenylene sulfide composition with improved crystallizing characteristic
WO2020171164A1 (fr) * 2019-02-22 2020-08-27 Dic株式会社 Composition à base de résine de poly(sulfure d'arylène), corps moulé de celle-ci, procédé de production d'une composition à base de résine de poly(sulfure d'arylène) et procédé de production d'un corps moulé

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