WO2024084884A1 - Article moulé par extraction forcée, composition de résine de polysulfure d'arylène et procédé de production d'article moulé par extraction forcée - Google Patents

Article moulé par extraction forcée, composition de résine de polysulfure d'arylène et procédé de production d'article moulé par extraction forcée Download PDF

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WO2024084884A1
WO2024084884A1 PCT/JP2023/034209 JP2023034209W WO2024084884A1 WO 2024084884 A1 WO2024084884 A1 WO 2024084884A1 JP 2023034209 W JP2023034209 W JP 2023034209W WO 2024084884 A1 WO2024084884 A1 WO 2024084884A1
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Prior art keywords
inorganic filler
parts
volume
resin composition
polyarylene sulfide
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PCT/JP2023/034209
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English (en)
Japanese (ja)
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隆平 黒川
昌志 國重
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Dic株式会社
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Publication of WO2024084884A1 publication Critical patent/WO2024084884A1/fr

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    • 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
    • B29C45/40—Removing or ejecting moulded articles
    • B29C45/44—Removing or ejecting moulded articles for undercut articles

Definitions

  • the present invention relates to a forced punch molded product, a polyarylene sulfide resin composition, and a method for producing the forced punch molded product.
  • PAS polyarylene sulfide
  • PPS polyphenylene sulfide
  • PAS resin is often used as a material for parts with complex shapes.
  • issues arise such as an increase in the number of parts, an increase in the number of manufacturing processes, and an increase in weak joints, so it is preferable to mold them as a single piece.
  • force-pull molding may be performed. In force-pull molding, the mold is pulled out in the axial direction over the bulge of the molded product, so the bulge of the molded product needs to deform inward appropriately (ideally elastically deform).
  • the problem that the present invention aims to solve is to provide a PAS molded product in which deformation of the cylindrical portion after force-punching is suppressed, a PAS resin composition capable of providing such a molded product, and a method for producing the same.
  • the forced punching molded product is A forced punch molded product having a cylindrical portion formed from a PAS resin composition obtained by blending a PAS resin (A) and an inorganic filler (B),
  • the cylindrical portion has an undercut-shaped bulge that protrudes radially outward at a tip portion thereof, the inner surface of the cylindrical portion has a step in the outer diameter direction at the tip portion, and the inner diameter of the cylindrical portion excluding the step has a gradient such that the inner diameter of the cylindrical portion increases toward the tip portion;
  • the inorganic filler (B) includes a powdery inorganic filler (B1),
  • the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A),
  • the tensile elastic modulus TD/MD ratio at 150° C. is 0.7 to 1.0.
  • the PAS resin composition comprises: A PAS resin composition for force-punching, comprising a PAS resin (A) and an inorganic filler (B),
  • the inorganic filler (B) contains a powdery inorganic filler (B1),
  • the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A),
  • the tensile modulus TD/MD ratio at 150° C. is 0.7 to 1.0.
  • a method for producing a PAS resin composition includes: A method for producing a PAS resin composition for force-punching, comprising a step of blending a PAS resin (A) and an inorganic filler (B) and melt-kneading the mixture at a temperature range equal to or higher than the melting point of the PAS resin (A),
  • the inorganic filler (B) contains a powdery inorganic filler (B1),
  • the amount of the powdered inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A).
  • the manufacturing method of the forced punch molded product manufactures the above-mentioned forced punch molded product by melt molding.
  • This disclosure relates to a method for using the above-described forced-removal molded product as a piping component that comes into contact with liquid or the above.
  • This disclosure makes it possible to provide a PAS punched-out molded product in which deformation of the cylindrical portion after punched-out molding is suppressed, a PAS resin composition capable of providing such a molded product, and a method for producing the same.
  • FIG. 1 is a perspective view of a main part of a force-punched molded product according to one embodiment of the present disclosure, and is a schematic diagram of the force-punched molded product used in the examples.
  • FIG. 2 is a cross-sectional view of a main part of the forced punching molded product of FIG.
  • FIG. 3 is a diagram for explaining the forced removal of the forced removal molded product of FIG.
  • FIG. 1 is a perspective view of the main part of the force-pulled molded product 1 according to this embodiment.
  • the main part of the force-pulled molded product 1 includes a cylindrical part 10 having a bulge part 11.
  • FIG. 2 is a cross-sectional view of the force-pulled molded product 1 taken along line A-A in FIG. 1.
  • the force-pulled molded product 1 is formed by injection molding a PAS resin composition and then forcing it out when it is demolded.
  • FIG. 3 is a diagram for explaining the force-pulling of the force-pulled molded product 1 in FIG. 1.
  • force-pulling refers to a molding method in which a mold 30 overcomes the bulge part 11 of the molded product and is pulled out in the axial direction.
  • the PAS resin composition is a composition obtained by blending a PAS resin with a fibrous filler. Details of the PAS resin composition will be described later.
  • the cylindrical portion 10 of the forced punch molded product 1 has an undercut bulge 11 that protrudes in the outer diameter direction in a certain range in the axial direction from the tip 15 (tip portion 16).
  • the cylindrical portion 10 has a cylindrical shape with two circular bottom surfaces centered on the axis CA, and both of the two bottom surfaces are open.
  • the cylindrical portion 10 has a hollow pipe shape with the tip 15 and the end 17 being open.
  • the outer diameter direction is a direction perpendicular to the axial direction, which is a direction along the axis CA, and is a direction from the axis CA toward the side.
  • the end 17 of the cylindrical portion 10 may be connected to another portion of the forced punch molded product 1. That is, the end 17 of the cylindrical portion 10 is located at a position axially farthest from the tip 15 such that the cross section has a circular shape centered on the axis CA.
  • the shape of the cylindrical portion 10 is symmetrical about the axis CA.
  • the two cross sections of the cylindrical portion 10 shown in FIG. 2 are vertically symmetrical about the axis CA.
  • the outer surface 21 of the cylindrical portion 10 extends in the axial direction from the end 17 toward the tip 15 until it reaches the tip portion 16.
  • the outer surface 21 then connects to the bulge portion 11 at the tip portion 16, where the apex 12 protrudes most in the outer radial direction.
  • the inner surface 22 of the cylindrical portion 10 has a step 13 in the outer diameter direction at the tip portion 16.
  • the inner surface 22 of the cylindrical portion 10 has a gradient such that the inner diameter of the cylindrical portion 10 increases as the portion excluding the step 13 moves from the end 17 to the tip portion 16. In this embodiment, the gradient is constant.
  • the portion of the inner surface 22 of the cylindrical portion 10 excluding the step 13 and the step 13 are connected at a connection portion 14.
  • the inclined portion 18 shown in FIG. 2 is the portion having a constant gradient from the end 17 to the tip portion 16, i.e., the portion of the inner surface 22 of the cylindrical portion 10 excluding the step 13.
  • the connection portion 14 is located at the end of the inclined portion 18 on the tip 15 side.
  • the cylindrical portion 10 having the bulge 11 is formed by force removal.
  • the mold 30 When demolding, the mold 30 is pulled out in the axial direction from the end 17 toward the tip portion 16. At this time, a force from the mold 30 is applied to the bulge 11, and the tip portion 16 bends toward the axis CA with the corner 14a at the step 13 as a fulcrum.
  • the value of the undercut rate is not limited.
  • the undercut rate may be preferably 20% or less, and more preferably 14% or less.
  • the undercut rate may be preferably 5% or more, and more preferably 3.5% or more.
  • undercut rate is determined by the following formula (c):
  • the outer diameter C in formula (c) is the outer diameter of the cylindrical portion 10 at the top 12 of the bulge portion 11, as shown in Figure 2.
  • the outer diameter B in formula (c) is the outer diameter of the cylindrical portion 10 excluding the bulge portion 11, as shown in FIG. 2.
  • the circularity retention rate of the cylindrical portion 10 of the force-punched molded product 1 according to this embodiment is preferably 90% or more, and more preferably 95% or more. This makes it possible to obtain a molded product with excellent appearance.
  • the circularity retention rate is a value calculated from the value measured by a dimension measuring machine using the method described in the examples.
  • the arithmetic mean height Sa of the inner wall surface of the bulge 11 is preferably 60 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the maximum height Sz of the inner wall surface of the bulge 11 is preferably 350 ⁇ m or less, and more preferably 300 ⁇ m or less.
  • the arithmetic mean height Sa and maximum height Sz are values measured according to the method described in the examples in accordance with ISO 25178.
  • the above-mentioned punched molded product 1 is formed from a PAS resin composition obtained by blending a PAS resin (A) and an inorganic filler (B).
  • the PAS resin composition described below (the PAS resin composition of the present disclosure) may be used exclusively for the punched molded product 1.
  • PAS resin composition of the present disclosure contains PAS resin (A) as an essential component.
  • PAS resin (A) has a resin structure with a repeating unit in which an aromatic ring and a sulfur atom are bonded, and specifically, is represented by 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, a structural portion represented by the following general formula (2):
  • the trifunctional structural unit represented by formula (2) is preferably in the range of 0.001 to 3 mol %, particularly preferably 0.01 to 1 mol %, based on the total number of moles of the trifunctional structural unit and other structural units.
  • the structural portion represented by the general formula (1) are preferably hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin.
  • examples of the structural portion 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).
  • a structure in which the bond of the sulfur atom to the aromatic ring in the repeating unit is bonded at the para position represented by the general formula (3) is particularly preferred in terms of heat resistance and crystallinity of the PAS resin.
  • the PAS resin has structural moieties represented by the general formulas (1) and (2) above, as well as the following structural formulas (5) to (8):
  • the structural moiety represented by the general formula (1) and the structural moiety represented by the general formula (2) may be contained in an amount of 30 mol % or less of the total of the structural moieties represented by the general formula (1) and the general formula (2).
  • the structural moieties represented by the general formulas (5) to (8) are 10 mol % or less in terms of the heat resistance and mechanical strength of the PAS resin.
  • the bonding mode thereof may be either a random copolymer or a block copolymer.
  • the PAS resin may have naphthyl sulfide bonds or the like in its molecular structure, but this is preferably 3 mol % or less, and more preferably 1 mol % or less, relative to the total number of moles including other structural parts.
  • a method for crosslinking PAS resin a method can be used in which a low molecular weight linear polymer obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogenated aromatic compound represented by the above general formula (1) is heated at high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by crosslinking or thermal crosslinking, or a method can be used in which a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen functional groups as represented by the above general formula (2) is used during condensation polymerization to partially form a branched structure or crosslinked structure.
  • the physical properties of the PAS resin (A) are not particularly limited as long as they do not impair the effects of the present invention, but are as follows:
  • the melt viscosity of the PAS resin (A) is not particularly limited, but in order to obtain a good balance between fluidity and mechanical strength, the melt viscosity (V6) measured at 300°C is preferably in the range of 2 Pa ⁇ s or more, and preferably in the range of 1000 Pa ⁇ s or less, more preferably in the range of 500 Pa ⁇ s or less, and further preferably in the range of 200 Pa ⁇ s or less.
  • the non-Newtonian index of the PAS resin (A) is not particularly limited, but is preferably in the range of 0.90 or more to 2.00 or less.
  • the non-Newtonian index is preferably in the range of 0.90 or more, more preferably in the range of 0.95 or more to preferably in the range of 1.50 or less, more preferably in the range of 1.20 or less.
  • Such a PAS resin is excellent in mechanical properties, fluidity, and abrasion resistance.
  • SR shear rate
  • SS shear stress
  • L orifice length
  • D orifice diameter
  • the method for producing the PAS resin (A) is not particularly limited, but examples thereof include (production method 1) a method in which a dihalogeno aromatic compound is polymerized in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component is added, (production method 2) a method in which a dihalogeno aromatic compound is polymerized in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerization component is added, (production method 3) a method in which p-chlorothiophenol is added, and if necessary, other copolymerization components are added, and self-condensed, and (production method 4) a method in which a diiodo aromatic compound and elemental sulfur are melt-polymerized under reduced pressure in the presence of a polymerization inhibitor that may have a functional group such as a carb
  • production method 2 is versatile and preferable.
  • an alkali metal salt of a carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization.
  • (Production Method 2) methods there is a method for producing a PAS resin by introducing a water-containing sulfidizing agent into a mixture containing a heated organic polar solvent and a dihalogeno-aromatic compound at a rate at which water can be removed from the reaction mixture, and reacting the dihalogeno-aromatic compound and the sulfidizing agent in the organic polar solvent, and optionally adding a polyhalogeno-aromatic compound, and controlling the amount of water in the reaction system to within a range of 0.02 to 0.5 moles per mole of the organic polar solvent (see JP-A-07-228699).
  • Particularly preferred is a method in which a dihalogeno-aromatic compound and, if necessary, a polyhalogeno-aromatic compound or other copolymerization component are added in the presence of potassium metal sulfide and an aprotic polar organic solvent, and an alkali metal hydrosulfide and an organic acid alkali metal salt are reacted while controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 mol per mol of the sulfur source and the amount of water in the reaction system to be 0.02 mol or less per mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet).
  • dihalogeno aromatic compound examples 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'-di
  • polyhalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahal
  • the method of post-treatment of the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited, but for example, (post-treatment 1) after the polymerization reaction is completed, first, the solvent is distilled off under reduced pressure or normal pressure, either as is or after adding an acid or base, and then the solid remaining after the solvent distillation is washed once or twice or more times with a solvent such as water, the reaction solvent (or an organic solvent having a similar solubility to the low molecular weight polymer), acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, filtered, and dried; or (post-treatment 2) after the polymerization reaction is completed, the reaction mixture is dissolved in a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, etc.
  • a solvent such as water, acetone, methyl ethy
  • (post-treatment 3) a method in which, after the completion of the polymerization reaction, a reaction solvent (or an organic solvent having a solubility equivalent to that of the low molecular weight polymer) is added to the reaction mixture, the mixture is stirred, the mixture is filtered to remove the low molecular weight polymer, the mixture is washed once or twice or more times with a solvent such as water, acetone, methyl ethyl ketone, or an alcohol, and then the mixture is neutralized, washed with water, filtered, and dried; (post-treatment 4) a method in which, after the completion of the polymerization reaction, water is added to the reaction mixture, the mixture is washed with water, filtered, and if necessary, an acid or a base is added during the water washing, and then the mixture is dried; or (post-treatment 5) a method in which, after the completion of the polymerization reaction,
  • the reactivity, crystallization rate, sodium content, etc. of the PAS resin can be controlled by adjusting the pH during the water washing process by adding an acid or base, and the pH after the hot water washing process can be controlled to be in the range of 6.5 to 11.5, more preferably in the range of 6.5 to 8.5.
  • the PAS resin may be dried in a vacuum, in air, or in an inert gas atmosphere such as nitrogen.
  • the PAS resin (A) used in this embodiment may be a PAS resin newly polymerized by the above method, or a recycled PAS resin.
  • a PAS resin recovered from a PAS resin composition or a PAS resin molded product may be used.
  • a PAS resin obtained by heating a PAS resin composition or a PAS resin molded product in an organic polar solvent to dissolve the PAS contained therein and then performing the above-mentioned post-treatment on the resulting solution may be used.
  • a PAS resin composition or a PAS resin molded product that has been mechanically crushed may be used as the PAS resin.
  • sprues or runners generated during the manufacture of molded products, products recovered as non-standard molded products, or crushed molded products that have been used as products may be used.
  • a crushed PAS resin composition or a PAS resin molded product that contains components other than PAS resin may be used.
  • the PAS resin composition of the present disclosure is prepared by blending an inorganic filler (B).
  • the inorganic filler (B) uses a powdered inorganic filler (B1) as an essential component. Furthermore, a plate-like inorganic filler (B2) and a fibrous inorganic filler (B3) can be used as optional components.
  • Materials for the inorganic filler (B) applicable to the present disclosure may be those known to those skilled in the art, and the fiber diameter, fiber length, and aspect ratio may be adjusted as appropriate depending on the application of the molded product.
  • the inorganic filler (B) applicable to the present disclosure may be one that has been treated with a surface treatment agent or a sizing agent. This is preferable because it can improve the adhesive strength with the PAS resin (A).
  • the surface treatment agent or sizing agent include at least one polymer selected from the group consisting of silane compounds having functional groups such as amino groups, epoxy groups, isocyanate groups, and vinyl groups, titanate compounds, acrylic resins, urethane resins, polyether resins, and epoxy resins, and those containing urethane resins are particularly preferable from the viewpoint of suppressing excessive defibration during processing.
  • the surface treatment agent or sizing agent contains urethane resin, the content is not particularly limited, but from the viewpoint of fuel swelling resistance, it is preferably in the range of 35 mass% or less, and more preferably in the range of 20 mass% or less.
  • the amount of inorganic filler (B) is preferably 40 parts by volume or more, more preferably 50 parts by volume or more, and even more preferably 60 parts by volume or more, per 100 parts by volume of PAS resin (A) from the viewpoint of obtaining better mechanical strength.
  • the amount is preferably 180 parts by volume or less, more preferably 140 parts by volume or less, and even more preferably 90 parts by volume or less.
  • the powdered and granular inorganic filler (B1) applicable to the present disclosure may be any known or commonly used material, and may include fillers of various shapes, such as plate-like and powdered fillers.
  • specific examples include graphite, silica, quartz powder, glass beads, silicates such as calcium silicate, aluminum silicate, and diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, and silicon carbide, silicon nitride, boron nitride, and various metal powders. One or more of these may be appropriately selected depending on the required performance. Of these, calcium carbonate and glass beads are preferably used.
  • the range of the average particle diameter ( D50 ) of the powdered inorganic filler (B1) applicable to the present disclosure is not particularly limited, but from the viewpoint of excellent mechanical strength and fluidity, it is preferably in the range of 100 ⁇ m or less, more preferably in the range of 50 ⁇ m or less, even more preferably in the range of 20 ⁇ m or less, and particularly preferably in the range of 2 ⁇ m or less.
  • the average particle diameter is the average particle diameter ( D50 ) obtained based on the particle size distribution measured according to a conventional method using a laser diffraction scattering type particle size distribution measuring instrument (Microtrac MT3300EXII).
  • the amount of powdered inorganic filler (B1) 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 is preferably in the range of 15 parts by volume or more, more preferably 30 parts by volume or more, and even more preferably 40 parts by volume or more, relative to 100 parts by volume of PAS resin (A), and is preferably in the range of 180 parts by volume or less, more preferably 140 parts by volume or less, and even more preferably 90 parts by volume or less. In such a range, the resin composition has good fuel swelling resistance and moldability, especially releasability, while the molded product exhibits high dimensional precision, which is preferable.
  • Plate-like inorganic filler (B2) applicable to the present disclosure may be any known or commonly used material, such as glass flakes, talc, mica, kaolin, clay, alumina, various metal foils, etc., and one or more types may be appropriately selected depending on the required performance. Among these, it is preferable to use glass flakes from the viewpoint of mechanical strength and ease of handling.
  • the amount of the plate-like inorganic filler (B2) 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 is preferably 80 parts by volume or less, more preferably 50 parts by volume or less, and even more preferably 10 parts by volume or less, per 100 parts by volume of the powdered inorganic filler (B1). In such a range, the resin composition has good fuel swelling resistance and moldability, especially releasability, while the molded product exhibits high dimensional precision, which is preferable.
  • Fiber-like inorganic fillers (B3) applicable to the present disclosure may be any known or commonly used material, such as glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite, and metal fibrous substances such as stainless steel, aluminum, titanium, copper, and brass, from which one or more types may be appropriately selected depending on the required performance. Among these, it is preferable to use glass fiber from the viewpoints of mechanical strength and ease of handling.
  • the amount of fibrous inorganic filler (B3) 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 is preferably 230 parts by volume or less, more preferably 130 parts by volume or less, even more preferably 100 parts by volume or less, and particularly preferably 20 parts by volume or less, per 100 parts by volume of the powdered inorganic filler (B1).
  • the resin composition has good fuel swelling resistance and moldability, especially releasability, while the molded product exhibits high dimensional precision, which is preferable.
  • the PAS resin composition of the present disclosure may contain a silane coupling agent as an optional component, if necessary.
  • the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but preferred examples include silane coupling agents 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.
  • silane coupling agents include epoxy group-containing alkoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylethyldimethoxysilane, ⁇ -isocyanatopropylethyldiethoxysilane, and ⁇ -isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such
  • the silane coupling agent is not an essential component, but when it is used, the amount of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, and is preferably in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, to preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). In such a range, the resin composition has good moldability, particularly releasability, and the mechanical strength of the molded product is improved, which is preferable.
  • the PAS resin composition of the present disclosure may contain a thermoplastic elastomer as an optional component, if necessary.
  • thermoplastic elastomers include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers, of which polyolefin-based elastomers are preferred.
  • their amount is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, to preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of PAS resin (A). This range is preferable because it improves the impact resistance of the resulting PAS resin composition.
  • the polyolefin-based elastomer may be a homopolymer of an ⁇ -olefin, a copolymer of two or more ⁇ -olefins, or a copolymer of one or more ⁇ -olefins and a vinyl polymerizable compound having a functional group.
  • examples of the ⁇ -olefin include ⁇ -olefins having 2 or more to 8 or less carbon atoms, such as ethylene, propylene, and 1-butene.
  • Examples of the vinyl polymerizable compound having the functional group include one or more of vinyl acetate; ⁇ , ⁇ -unsaturated carboxylic acids such as (meth)acrylic acid; alkyl esters of ⁇ , ⁇ -unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate; metal salts of ⁇ , ⁇ -unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, and zinc); glycidyl esters of ⁇ , ⁇ -unsaturated carboxylic acids such as glycidyl methacrylate; ⁇ , ⁇ -unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and derivatives of the ⁇ , ⁇ -unsaturated dicarboxylic acids (monoesters, diesters, and acid anhydrides).
  • the PAS resin composition of the present disclosure may contain synthetic resins such as polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylate resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenolic resin, urethane resin, and liquid crystal polymer (hereinafter simply referred to as synthetic resin) as optional components depending on the application.
  • synthetic resins such as polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylate resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene
  • the synthetic resin is not an essential component, but when it is added, the ratio of the synthetic resin is not particularly limited as long as it does not impair the effects of the present invention, and it differs depending on each purpose and cannot be generally defined, but the ratio of the synthetic resin to be added in the resin composition of the present disclosure is, for example, in the range of 5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of PAS resin (A).
  • 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, based on mass.
  • the PAS resin composition of the present disclosure may also contain other known and commonly used additives, such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, and release agents (metal salts or esters of fatty acids having 18 to 30 carbon atoms, including stearic acid or montanic acid, polyolefin waxes such as polyethylene, etc.), as optional components, as necessary.
  • additives such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, and release agents (metal salts or esters of fatty acids having 18 to 30 carbon atoms, including stearic acid or montanic acid, polyolefin waxes such as polyethylene, etc.
  • additives are not essential components, and may be used in an amount of, for example, preferably 0.01 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the PAS resin (A), as appropriate for the purpose or application so as not to impair the effects of the present invention.
  • the PAS resin composition of the present disclosure has a small anisotropy of the tensile modulus at 150°C. Specifically, the TD/MD ratio is in the range of 0.7 to 1.0. In this range, deformation of the molded product before and after the force-pulling process in the molding process can be suppressed, and the dimensional accuracy is excellent.
  • it is effective to adjust the amount of inorganic filler (B), which can be achieved by, for example, adjusting the amount of powdered inorganic filler (B1), which is an essential component, and plate-like inorganic filler (B2) and fibrous inorganic filler (B3), which are optional components.
  • the TD/MD ratio of the tensile modulus at 150°C in this disclosure is a value measured in accordance with the method of the examples.
  • MD refers to the flow direction of the resin in molding, and refers to a direction with a fiber orientation parameter of 0.9 or more.
  • TD refers to a direction perpendicular to the flow direction of the resin in molding, and refers to a direction with a fiber orientation parameter of 0.1 or less. The closer the TD/MD ratio is to 1, the smaller the anisotropy of the elastic modulus is.
  • the tensile modulus of the PAS resin composition of the present disclosure at room temperature (23°C) is not particularly limited, but is preferably 15 GPa or less, and more preferably 8 GPa or less. This range is preferable because it can suppress deformation of the molded product before and after the force-pulling process in the molding process, and provides excellent dimensional accuracy.
  • the tensile modulus in this disclosure is a value measured using an ISO Type-A dumbbell piece obtained by injection molding the PAS resin composition, using a method conforming to ISO 527-1 and 2.
  • the method for producing a PAS resin composition disclosed herein is a method for producing a PAS resin composition for force-punch molding, which comprises a step of blending PAS resin (A) and inorganic filler (B) as essential components and melt-kneading them at a temperature range equal to or higher than the melting point of PAS resin (A), characterized in that the inorganic filler (B) contains a powdered inorganic filler (B1), and the powdered inorganic filler (B1) is present in an amount of 15 to 180 parts by volume per 100 parts by volume of the PAS resin (A). This is described in detail below.
  • the method for producing the PAS resin composition of the present disclosure includes a step of blending the above essential components and melt-kneading them at 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 is composed of each essential component and, if necessary, other optional components.
  • Methods for producing resin compositions that can be applied to the present disclosure include, but are not limited to, a method of blending the essential components and, if necessary, optional components, and melt-kneading them, and more specifically, a method of uniformly dry-mixing them in a tumbler or Henschel mixer, if necessary, and then feeding them into a twin-screw extruder and melt-kneading them.
  • the melt kneading can be carried out by heating the resin to a temperature range in which the resin temperature is equal to or higher than the melting point of the PAS resin (A), preferably equal to or higher than the melting point + 10°C, more preferably equal to or higher than the melting point + 10°C, even more preferably equal to or higher than the melting point + 20°C, preferably equal to or lower than the melting point + 100°C, more preferably equal to or lower than the melting point + 50°C.
  • the melt kneader is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity.
  • the addition and mixing of each component to the melt kneader may be performed simultaneously or in portions.
  • the inorganic filler (B) when adding the inorganic filler (B), which is an essential component among the components, it can be fed into the extruder from a side feeder of the twin-screw kneading extruder.
  • the position of the side feeder is preferably such that the ratio of the distance from the extruder resin input section (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, and more preferably 0.3 or more. In addition, such a ratio is preferably 0.9 or less, and more preferably 0.7 or less.
  • the PAS resin composition of the present disclosure obtained by melt kneading in this manner is a molten mixture containing the essential components, optional components added as necessary, and components derived from these. Therefore, the PAS resin composition of the present disclosure has a morphology in which the PAS resin (A) forms a continuous phase and the other essential components and optional components are dispersed.
  • the PAS resin composition of the present disclosure is preferably processed into pellets, chips, granules, powder, or other forms by a known method, for example, by extruding the molten resin composition into strands, and then pre-dried at a temperature range of 100 to 150°C as necessary.
  • the molded article of the present disclosure is produced by melt molding a PAS resin composition.
  • the manufacturing method of the molded article of the present disclosure also includes 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 and optional components are dispersed.
  • the PAS resin composition having such a morphology allows for the production of a molded article with excellent fuel swelling resistance and mechanical strength.
  • the PAS resin composition disclosed herein can be subjected to various molding processes such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding applications due to its excellent releasability.
  • various molding conditions are not particularly limited, and molding can be performed by a normal general method.
  • the PAS resin composition is melted at a resin temperature in a temperature range of the melting point of the PAS resin (A) or higher, preferably in a temperature range of the melting point + 10°C or higher, more preferably in a temperature range of the melting point + 10°C to the melting point + 100°C, and even more preferably in a temperature range of the melting point + 20 to the melting point + 50°C, and then the resin is injected into a mold from a resin outlet and molded.
  • the mold temperature may also be set to a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.
  • the manufacturing method of the PAS resin molded product disclosed herein includes a step of annealing the molded product.
  • the optimum conditions for the annealing treatment are selected depending on the application or shape of the molded product, and the annealing temperature is preferably in the range of 100°C or more, and more preferably in the range of 120°C or more. On the other hand, it is preferably in the range of 260°C or less, and more preferably in the range of 240°C or less.
  • the annealing time is not particularly limited, but is preferably in the range of 0.5 hours or more, and more preferably in the range of 1 hour or more. On the other hand, it is preferably in the range of 10 hours or less, and more preferably in the range of 8 hours or less. In such a range, distortion of the obtained molded product is reduced and the crystallinity of the resin is improved, which is preferable.
  • the annealing treatment may be performed in air, but is preferably performed in an inert gas such as
  • the molded product according to this embodiment includes a remolded product obtained by reusing a molded product obtained by melt-molding the PAS resin composition. Specifically, for example, it includes a sprue or runner generated during the manufacture of a molded product, a molded product recovered as a non-standard molded product, or a molded product once used as a product, which is washed as necessary, crushed, and melt-molded again at a temperature equal to or higher than the melting point of the PAS resin. When reusing, it is preferable from the viewpoint of mechanical properties to mix the crushed molded product with the PAS resin composition.
  • the size of the molded product when crushed is not particularly limited, but from the viewpoint of mixability and processability, it is preferable that the size is about the same as that of the PAS resin composition to be mixed.
  • the mixing ratio is preferably 50 parts by mass or less of the crushed molded product per 100 parts by mass of the PAS resin composition, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less. Within such a range, recyclability can be improved without impairing the effects of the PAS resin composition of the present disclosure.
  • the PAS resin molded product of the present disclosure is characterized by its excellent force-pullability, and is therefore particularly suitable for parts made using a force-pull mold.
  • Examples include piping, containers, joints, valve bodies, etc., and more specifically, it can be used for various parts that come into contact with liquid or steam, such as pipes, lining pipes, cap nuts, pipe joints (elbows, headers, tees, reducers, joints, couplers, etc.), various valves, flow meters, gaskets (seals, packings), etc.
  • the molded product of the present disclosure can also be made into ordinary resin molded products such as the following:
  • electrical and electronic components such as protective and supporting members for box-shaped integrated modules of electrical and electronic components, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor 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 crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related components, etc.; VTR components, television components, irons, hair dryers, rice cooker components, microwave oven components, Home and office electrical appliance parts such as audio parts, audio/visual equipment parts such as audio/laser discs, compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and water-
  • Examples 1 to 7 and Comparative Examples 1 to 4 Each material was blended according to the composition and blending amounts shown in Tables 1 and 2. Then, these blended materials were fed into a vented twin-screw extruder "TEX-30 ⁇ (product name)" manufactured by Japan Steel Works, Ltd., and melt-kneaded at a resin component discharge rate of 30 kg/hr, a screw rotation speed of 200 rpm, and a set resin temperature of 320°C to obtain pellets of the resin composition.
  • the glass fiber was fed from a side feeder (S/T ratio 0.5), and the other materials were mixed uniformly in advance in a tumbler and fed from a top feeder.
  • the pellets of the obtained resin composition were dried in a gear oven at 140°C for 2 hours, and then injection molded to prepare various test pieces, and the following tests were performed.
  • PAS resin (A) PPS resin A-1 Linear type, melt viscosity (V6) 40 Pa ⁇ s, non-Newtonian index 1.16
  • Tables 1 and 2 show that the molded products of the examples have smaller surface roughness and a higher rate of circularity retention than the molded products of the comparative examples, which makes it clear that deformation during forced punch molding is suppressed.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne : un article moulé en poly(sulfure d'arylène) (PAS) ayant une partie cylindrique résistante à la déformation soumise à un moulage par extraction forcée ; une composition de résine PAS qui permet d'obtenir ledit article moulé ; et son procédé de production. Plus particulièrement, la présente invention concerne : un article moulé par extraction forcée formé pour avoir une partie cylindrique à partir d'une composition de résine PAS obtenue par mélange d'une résine PAS et d'une charge inorganique, la partie cylindrique ayant un renflement en forme de contre-dépouille faisant saillie dans une direction radiale externe au niveau d'une partie pointe, la surface interne de la partie cylindrique ayant une marche dans la direction radiale externe au niveau de la partie pointe, la partie excluant la marche ayant une pente inclinée de telle sorte que le diamètre interne de la partie cylindrique augmente vers la partie pointe, la charge inorganique comprenant une charge inorganique pulvérulente, la quantité de la charge inorganique pulvérulente étant de 15 à 180 parties en volume par rapport à 100 parties en volume de la résine PAS et le rapport TD/MD du module de traction à 150 °C étant de 0,7 à 1,0 ; une composition de résine PAS pour moulage par extraction forcée ; et son procédé de production.
PCT/JP2023/034209 2022-10-18 2023-09-21 Article moulé par extraction forcée, composition de résine de polysulfure d'arylène et procédé de production d'article moulé par extraction forcée WO2024084884A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002021854A (ja) * 2000-07-11 2002-01-23 Koyo Seiko Co Ltd 転がり軸受用保持器
JP2015013984A (ja) * 2013-06-05 2015-01-22 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及び成形体
JP2018141083A (ja) * 2017-02-28 2018-09-13 東レ株式会社 無理抜き射出成形用ポリフェニレンスルフィド樹脂組成物
WO2019045032A1 (fr) * 2017-08-31 2019-03-07 ポリプラスチックス株式会社 Composition de résine, article moulé et procédé de production dudit article moulé
WO2022075124A1 (fr) * 2020-10-05 2022-04-14 Dic株式会社 Article moulé par extraction forcée, composition de résine de polysulfure d'arylène et procédé de production d'article moulé par extraction forcée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002021854A (ja) * 2000-07-11 2002-01-23 Koyo Seiko Co Ltd 転がり軸受用保持器
JP2015013984A (ja) * 2013-06-05 2015-01-22 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及び成形体
JP2018141083A (ja) * 2017-02-28 2018-09-13 東レ株式会社 無理抜き射出成形用ポリフェニレンスルフィド樹脂組成物
WO2019045032A1 (fr) * 2017-08-31 2019-03-07 ポリプラスチックス株式会社 Composition de résine, article moulé et procédé de production dudit article moulé
WO2022075124A1 (fr) * 2020-10-05 2022-04-14 Dic株式会社 Article moulé par extraction forcée, composition de résine de polysulfure d'arylène et procédé de production d'article moulé par extraction forcée

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