WO2024084884A1 - Forced extraction molded article, polyarylene sulfide resin composition and method for producing forced extraction molded article - Google Patents

Abstract

Provided are: a polyarylene sulfide (PAS) molded article having a deformation-resistant cylindrical portion subjected to forced extraction molding; a PAS resin composition that can afford said molded article; and a method for producing same. More specifically, the present invention provides: a forced extraction molded article formed to have a cylindrical portion from a PAS resin composition obtained by mixing a PAS resin and an inorganic filler, wherein the cylindrical portion has an undercut-shaped bulge protruding in an outer radial direction at a tip portion, the inner surface of the cylindrical portion has a step in the outer radial direction at the tip portion, the portion excluding the step has a slope inclined such that the inner diameter of the cylindrical portion increases toward the tip portion, the inorganic filler includes a powdery inorganic filler, the amount of the powdery inorganic filler is 15-180 parts by volume relative to 100 parts by volume of the PAS resin, and the TD/MD ratio of tensile modulus at 150°C is 0.7-1.0; a PAS resin composition for forced extraction molding; and a method for producing same.

Description

Forced punching molded product, polyarylene sulfide resin composition, and method for producing forced punching molded product

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.

In recent years, engineering plastics have been developed that are highly heat-resistant and have excellent productivity and moldability. Because they are lightweight, they are widely used as alternatives to metal materials in electrical and electronic equipment and automobiles. In particular, polyarylene sulfide (PAS) resins, such as polyphenylene sulfide (PPS), are widely used in fields such as automotive parts and electrical and electronic equipment because they have excellent heat resistance, mechanical strength, chemical resistance, moldability, and dimensional stability.

PAS resin is often used as a material for parts with complex shapes. When assembling multiple parts to construct 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. When molding as a single piece, for example, for piping parts with a bulge at the tip, 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).

In relation to the above, a resin composition for use in forced punch molded products has been proposed that prevents deformation from remaining in molded products that have been subjected to force punch molding by specifying the flexural modulus of the resin composition (for example, Patent Document 1).

International Publication No. 2019/045032

However, these methods do not adequately suppress deformation during forced punching of resin molded products, and further improvements are needed.

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.

As a result of extensive research into solving the above problems, the inventors discovered that by combining a specific amount of filler with PAS resin, deformation of the cylindrical portion of a PAS resin molded product after forced punch molding can be suppressed, which led to the completion of the present invention.

That is, the forced punching molded product according to one embodiment of the present disclosure 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; and 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 according to one embodiment of the present disclosure 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 according to one embodiment of the present disclosure 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 according to one embodiment of the present disclosure 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.

<Forced punching molded products>
Hereinafter, a force-punched molded product 1 according to an embodiment of the present disclosure will be described with reference to the drawings. In the drawings used in the following description, the shapes and dimensional relationships of the elements shown may differ from the shapes and dimensional relationships of the actual force-punched molded product 1.

FIG. 1 is a perspective view of the main part of the force-pulled molded product 1 according to this embodiment. In 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. Here, 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.

In this embodiment, 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). Here, 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. In other words, 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.

As shown in FIG. 1, 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. Here, the shape of the cylindrical portion 10 is symmetrical about the axis CA. For example, the two cross sections of the cylindrical portion 10 shown in FIG. 2 are vertically symmetrical about the axis CA.

As shown in FIG. 2, 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. Here, 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.

As shown in Figure 3, the cylindrical portion 10 having the bulge 11 is formed by force removal. 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.

In this embodiment, the value of the undercut rate is not limited. However, from the viewpoint of preventing molding defects such as breakage due to elastic deformation of the bulge portion 11 during forced punch molding, the undercut rate may be preferably 20% or less, and more preferably 14% or less. Furthermore, from the viewpoint of preventing the bulge portion 11 from coming out when inserted into a flexible tube or pipe, etc., the undercut rate may be preferably 5% or more, and more preferably 3.5% or more.

Here, the 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.

In the force-punched molded product 1 according to this embodiment, the arithmetic mean height Sa of the inner wall surface of the bulge 11 is preferably 60 μm or less, and more preferably 50 μm or less. Also, the maximum height Sz of the inner wall surface of the bulge 11 is preferably 350 μm or less, and more preferably 300 μm 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.

<PAS resin composition>
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.

The 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):

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１～４の範囲のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）で表される構造部位と、必要に応じてさらに下記一般式（２）

(wherein 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):

で表される３官能性の構造部位と、を繰り返し単位とする樹脂である。式（２）で表される３官能性の構造部位は、他の構造部位との合計モル数に対して０．００１～３モル％の範囲が好ましく、特に０．０１～１モル％の範囲であることが好ましい。

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.

Here, the structural portion represented by the general formula (1), particularly ^R1 and ^R2 in the formula, are preferably hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin. In this case, 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).

　これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記一般式（３）で表されるパラ位で結合した構造であることが前記ＰＡＳ樹脂の耐熱性や結晶性の面で好ましい。

Among these, 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):

で表される構造部位を、前記一般式（１）と一般式（２）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本開示では上記一般式（５）～（８）で表される構造部位は１０モル％以下であることが、ＰＡＳ樹脂の耐熱性、機械的強度の点から好ましい。前記ＰＡＳ樹脂中に、上記一般式（５）～（８）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。

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). In particular, in the present disclosure, it is preferable that 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. When the structural moieties represented by the general formulas (5) to (8) are contained in 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.

As 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:

(Melt Viscosity)
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. However, the melt viscosity (V6) is measured by using a flow tester, CFT-500D manufactured by Shimadzu Corporation, and is the measured value of the melt viscosity after holding the PAS resin at 300°C, a load of 1.96×10 ⁶ Pa, and L/D=10 (mm)/1 (mm) for 6 minutes.

(Non-Newtonian Exponents)
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. When a linear type PAS resin is used, 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. However, the non-Newtonian index (N value) is a value calculated using the following formula by measuring the shear rate (SR) and shear stress (SS) using a capillary rheometer under the conditions of melting point +20 ° C. and the ratio of the orifice length (L) to the orifice diameter (D), L / D = 40. The closer the non-Newtonian index (N value) is to 1, the closer the structure is to a linear structure, and the higher the non-Newtonian index (N value), the more branched the structure is.

［ただし、ＳＲは剪断速度（秒^－１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］

[where SR is the shear rate (sec ^-1 ), SS is the shear stress (dynes/ ^cm2 ), and K is a constant.]

(Method for producing PAS resin)
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 carboxy group or an amino group. Among these methods, (production method 2) is versatile and preferable. During the reaction, an alkali metal salt of a carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above-mentioned (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). Specific examples of the dihalogeno aromatic compound 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 Examples of the 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-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. The halogen atoms contained in the above compounds are preferably chlorine atoms or bromine atoms.

　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 that is soluble in the polymerization solvent used and is a poor solvent for at least PAS). or (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 reaction mixture is filtered, and if necessary, the mixture is washed once or twice or more times with the reaction solvent, and then the mixture is washed with water, filtered, and dried. In either post-treatment method, 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.

In the post-treatment methods exemplified above in (Post-treatment 1) to (Post-treatment 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. For example, a PAS resin recovered from a PAS resin composition or a PAS resin molded product may be used. Specifically, 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. In addition, a PAS resin composition or a PAS resin molded product that has been mechanically crushed may be used as the PAS resin. Specifically, 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. In this case, a crushed PAS resin composition or a PAS resin molded product that contains components other than PAS resin may be used.

<Inorganic filler (B)>
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). Examples of 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. When 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. On the other hand, from the viewpoint of the fluidity and processability of the resin composition, 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 μm or less, more preferably in the range of 50 μm or less, even more preferably in the range of 20 μm or less, and particularly preferably in the range of 2 μm 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). 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.

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. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. In the present disclosure, 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. Examples of thermoplastic elastomers include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers, of which polyolefin-based elastomers are preferred. When these elastomers are added, 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.

For example, the polyolefin-based elastomer may be a homopolymer of an α-olefin, a copolymer of two or more α-olefins, or a copolymer of one or more α-olefins and a vinyl polymerizable compound having a functional group. In this case, examples of the α-olefin include α-olefins having 2 or more to 8 or less carbon atoms, such as ethylene, propylene, and 1-butene. Examples of the functional group include a carboxy group, an acid anhydride group (-C(=O)OC(=O)-), an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and an oxazoline group. Examples of the vinyl polymerizable compound having the functional group include one or more of vinyl acetate; α,β-unsaturated carboxylic acids such as (meth)acrylic acid; alkyl esters of α,β-unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate; metal salts of α,β-unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, and zinc); glycidyl esters of α,β-unsaturated carboxylic acids such as glycidyl methacrylate; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and derivatives of the α,β-unsaturated dicarboxylic acids (monoesters, diesters, and acid anhydrides). The above-mentioned thermoplastic elastomers may be used alone or in combination of two or more.

In addition to the above components, 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. In the present disclosure, 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). 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, 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. These 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. In order for the PAS resin composition to have the above properties, 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. In this disclosure, 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. On the other hand, 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. For example, it is preferable to melt knead while appropriately adjusting the resin component discharge rate in the range of 5 to 500 (kg/hr) and the screw rotation speed in the range of 50 to 500 (rpm), and it is even more preferable to melt knead under conditions where the ratio (discharge rate/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). In addition, the addition and mixing of each component to the melt kneader may be performed simultaneously or in portions. For example, 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. After the melt kneading, 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. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a normal general method. For example, in an injection molding machine, 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. At that time, 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 nitrogen gas.

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. In addition, 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. In addition, the molded product of the present disclosure can also be made into ordinary resin molded products such as the following: For example, 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-related equipment parts such as water heaters, bath water volume sensors, and temperature sensors; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, and other machine related parts; optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, and clocks; alternator terminals, alternator connectors, brush holders, slip rings, I C regulators, potentiometer bases for light dimmers, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel, exhaust systems and intake systems, air intake nozzle snorkels, intake manifolds, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, water Examples of automobile and vehicle-related parts include pump impellers, turbine vanes, wiper motor-related parts, distributors, starter switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases, and can also be used for a variety of other purposes.

The following describes the present invention using examples and comparative examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "%" and "parts" are based on volume.

<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-30α (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.

＜Evaluation＞

(1) Evaluation of tensile properties The obtained pellets were fed to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a cylinder temperature set to 310 ° C., and injection molding was performed using an ISO Type-A dumbbell piece molding die with a mold temperature controlled to 140 ° C. to obtain an ISO Type-A dumbbell piece. The resin was injected from a single gate so that the test piece did not include a welded portion. The tensile modulus and tensile elongation at break of the obtained dumbbell piece at room temperature were measured by a measurement method based on ISO 527-1 and 2. The results are shown in Tables 1 and 2.

(2) Measurement of TD/MD ratio of tensile modulus at 150 ° C. Injection molding was performed using a 100 × 100 × 2 mmt molding die under the same conditions as in (1) to obtain a sheet-shaped molded product. Using the obtained molded product, a tensile test dumbbell (ISO Type 1BA) was cut in the resin flow direction (MD direction) and in the direction perpendicular to the MD direction (TD direction). The obtained dumbbell pieces were measured for tensile modulus at 150 ° C. by a measurement method based on ISO 527-1 and 2, and the TD/MD ratio was calculated. The results are shown in Tables 1 and 2.

(3) Measurement of surface roughness (Sa and Sz) of forced-pullout molded product The obtained pellets were fed to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a cylinder temperature set to 310 ° C., and injection molded using a mold having a forced-pullout structure with a mold temperature controlled to 140 ° C. to obtain a molded product in a pipe shape (inner diameter φ11.5, undercut ratio 15). The presence or absence of cracks on the inner diameter side surface of the pipe tip was visually confirmed, and if there were cracks, the surface roughness (arithmetic mean height Sa and maximum height Sz) of the cracked part was measured in accordance with ISO 25178 using a 3D dimension measuring machine (Keyence Corporation "VR-5200"). If a large and deep crack occurred, Sa and Sz showed larger values. The results are shown in Tables 1 and 2.

(4) Evaluation of the roundness retention rate of the forced punched molded product Evaluation was performed using a molded product of the same pipe shape as in (3). The outer diameter direction dimension from the tip of the cylindrical part to the top of the bulge part at the point (a) where the inner diameter side inclination of the pipe tip is the largest and the point (b) where the inner diameter side inclination is the smallest (the dimension from the tip 15 of the cylindrical part 10 to the top 12 of the bulge part 11 in FIG. 2) was measured using a 3D dimension measuring machine "VR-5200" manufactured by Keyence Corporation. From the measured value, the roundness was calculated by the following formula. The closer the roundness is to 100%, the more the deformation is suppressed. The results are shown in Tables 1 and 2.
Roundness retention rate [%] = (b) dimension [mm] / (a) dimension [mm] x 100

PAS resin (A)
PPS resin A-1: Linear type, melt viscosity (V6) 40 Pa·s, non-Newtonian index 1.16

Inorganic filler (B)
B-1: Powdered inorganic filler, glass beads, UB-02EG manufactured by Union Co., Ltd., particle size (D ₅₀ ) 19.5 μm
B-2: Powdered inorganic filler, calcium carbonate, calcium carbonate grade 1 manufactured by Sankyo Seifun Co., Ltd., particle size (D ₅₀ ) 1.7 μm
B-3: Plate-shaped inorganic filler, glass flake, Nippon Sheet Glass Co., Ltd. REFG-301, base flake average particle size 160 μm, thickness 5 μm
B-4: Fibrous inorganic filler, glass fiber, Nippon Electric Glass Co., Ltd. ECS03T-725H, fiber diameter: 10 μm, fiber length: chopped strand of 3 mm

Other components C-1: Elastomer Bondfast 7L manufactured by Sumitomo Chemical Co., Ltd.

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.

REFERENCE SIGNS LIST 1 Forced pull-out molded product 10 Cylindrical portion 11 Bulging portion 12 Top portion 13 Step 14 Connection portion 14a Corner portion 15 Tip 16 Tip portion 17 End portion 18 Sloping portion 21 Outer surface 22 Inner surface 30 Mold

Claims (14)

A forced punch molded product having a cylindrical portion formed from a polyarylene sulfide resin composition obtained by blending a polyarylene sulfide 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 has a gradient such that the inner diameter of the cylindrical portion increases toward the tip portion except for the step; and the inorganic filler (B) includes a powdery inorganic filler (B1),
the powdered inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the polyarylene sulfide resin (A);
A punched product having a TD/MD ratio of tensile modulus at 150°C of 0.7 to 1.0. Furthermore, the inorganic filler (B) contains at least a plate-like inorganic filler (B2),
2. The force-punched molded product according to claim 1, wherein the plate-like inorganic filler (B2) is in the range of 60 parts by volume or less per 100 parts by volume of the powdery inorganic filler (B1). Furthermore, the inorganic filler (B) contains at least a fibrous inorganic filler (B3),
3. The force-punched molded product according to claim 1, wherein the amount of the fibrous inorganic filler (B3) is in the range of 230 parts by volume or less per 100 parts by volume of the powdery inorganic filler (B1). The force-punched molded product according to claim 1 or 2, wherein the circularity retention rate of the cylindrical portion is 90% or more. (The circularity retention rate is calculated by measuring the outer diameter direction dimensions from the tip of the cylindrical portion to the top of the bulge at the point (a) where the inner diameter side inclination of the cylindrical portion is the largest and the point (b) where the inner diameter side inclination is the smallest, using a dimension measuring machine, and calculating the circularity retention rate from the following formula.)
Roundness retention rate [%] = (b) dimension [mm] / (a) dimension [mm] x 100 The punched product according to claim 1 or 2, in which the arithmetic mean height Sa of the inner wall of the bulge, measured by a dimension measuring device, is 60 [μm] or less, and the maximum height Sz is 350 [μm] or less. A polyarylene sulfide resin composition for force-punching, comprising a polyarylene sulfide resin (A) and an inorganic filler (B),
The inorganic filler (B) contains a powdery inorganic filler (B1),
the powdered inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the polyarylene sulfide resin (A);
A polyarylene sulfide resin composition for force-punching, characterized in that the TD/MD ratio of the tensile modulus at 150°C is 0.7 to 1.0. Furthermore, the inorganic filler (B) contains a plate-like inorganic filler (B2),
7. The polyarylene sulfide resin composition for force-punching according to claim 6, wherein the amount of the plate-like inorganic filler (B2) is in the range of 60 parts by volume or less per 100 parts by volume of the powdery or granular inorganic filler (B1). Furthermore, the inorganic filler (B) includes one of fibrous inorganic fillers (B3),
8. The polyarylene sulfide resin composition for force-punching according to claim 6, wherein the amount of the fibrous inorganic filler (B3) is in the range of 230 parts by volume or less per 100 parts by volume of the powdery inorganic filler (B1). The polyarylene sulfide resin composition for force-punching according to claim 6 or 7, which is a melt-kneaded product. A method for producing a polyarylene sulfide resin composition for force-punching, comprising a step of blending a polyarylene sulfide 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 polyarylene sulfide resin (A),
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 polyarylene sulfide resin (A);
A method for producing a polyarylene sulfide resin composition for force-punching, comprising the steps of: Furthermore, the inorganic filler (B) contains a plate-like inorganic filler (B2),
11. The method for producing a polyarylene sulfide resin composition for force-punching according to claim 10, characterized in that the amount of the plate-like inorganic filler (B2) is in the range of 60 parts by volume or less per 100 parts by volume of the powdery inorganic filler (B1). Furthermore, the inorganic filler (B) contains a fibrous inorganic filler (B3),
12. The method for producing a polyarylene sulfide resin composition for force-punch molding according to claim 10 or 11, characterized in that the amount of the fibrous inorganic filler (B3) is in the range of 230 parts by volume or less per 100 parts by volume of the powdery inorganic filler (B1). A method for producing a forced-pull molded product, comprising the steps of producing a polyarylene sulfide resin composition by the method described in claim 10 or 11, and performing injection molding using a mold having a forced-pull structure. A method for using the forced-punch molded product according to claim 1 or 2 as a component that comes into contact with liquid or steam.

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