Forced-mold-release molded article, polyarylene sulfide resin composition, and method for producing forced-mold-release molded article

Abstract

Provided are: a polyarylene sulfide (PAS) molded article in which deformation of a cylindrical portion after forced mold release molding is suppressed; a PAS resin composition capable of providing the molded article; and a method for producing the PAS resin composition and the polyarylene sulfide molded article. The present invention relates to a forced mold release molded article, and more specifically, to a forced mold release molded article, a PAS resin composition for forced mold release molding, and a method for manufacturing the same, the forced mold release molded article being formed from a PAS resin composition obtained by blending a PAS resin and an inorganic filler so as to have a cylindrical portion, the cylindrical portion has an undercut-shaped bulge portion protruding in the outer diameter direction at the tip portion, the inner surface of the cylindrical portion has a step in the outer diameter direction at the tip portion, and the portion other than the step has a gradient inclined so that the inner diameter of the cylindrical portion increases toward the tip portion. The inorganic filler contains a particulate inorganic filler, the amount of the particulate inorganic filler is 15-180 parts by volume per 100 parts by volume of the PAS resin, and the TD / MD ratio of the tensile modulus at 150 DEG C of the polyarylene sulfide resin composition is 0.7-1.0.

Description

Technical Field

[0001] The present invention relates to a forced demolding molded product, a polyarylene sulfide resin composition and a method for producing the forced demolding molded product. Background Art

[0002] In recent years, engineering plastics with excellent productivity and moldability and high heat resistance have been developed, and they are also lightweight, and therefore are widely used as materials to replace metal materials for components of electrical and electronic equipment, automobile applications, etc. In particular, polyarylene sulfide (hereinafter, sometimes abbreviated as PAS) resins represented by polyphenylene sulfide (hereinafter, sometimes abbreviated as PPS) resins have excellent heat resistance, mechanical strength, chemical resistance, moldability, and dimensional stability, and therefore are widely used in the fields of automobile parts, electrical and electronic applications.

[0003] PAS resin is also often used as a material for parts with complex shapes. When a plurality of components are combined to form a part with a complex shape, the increase in the number of components, the increase in the number of manufacturing processes, the increase in fragile joints, etc. become issues, and therefore, it is preferred to perform one-piece molding. In the case of one-piece molding, for example, in piping components with a bulging portion at the front end, forced demolding is sometimes performed. In forced demolding, the mold is pulled axially over the bulging portion of the molded product, and therefore, the bulging portion of the molded product must be appropriately deformed inward (ideally elastically deformed).

[0004] In connection with the above, a resin composition for a forced-release molded product has been proposed that limits the flexural modulus of the resin composition to prevent deformation from remaining in a molded product subjected to forced-release molding (for example, Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2019 / 045032 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] However, the suppression of deformation of resin molded products obtained by these methods during forced demolding is not sufficient, and further improvement is required.

[0010] Therefore, an object of the present invention is to provide a PAS molded product in which deformation of a cylindrical portion after forced demolding is suppressed, a PAS resin composition capable of providing the molded product, and a method for producing the same.

[0011] Solutions for solving problems

[0012] The present inventors have conducted intensive studies to solve the above problems and have found that deformation of the cylindrical portion of a PAS resin molded product after forced demolding is suppressed by combining a specific amount of filler with a PAS resin, thereby completing the present invention.

[0013] That is, the forced demolding molded product according to one embodiment of the present disclosure is characterized in that:

[0014] In the forced demolding molded article, a PAS resin composition obtained by mixing a PAS resin (A) and an inorganic filler (B) is formed into a cylindrical portion.

[0015] The cylindrical portion has a bulging portion in the shape of an undercut protruding in the outer diameter direction at the front end portion.

[0016] The inner surface of the cylindrical portion has a step in the outer diameter direction at the front end portion, and the portion of the inner surface of the cylindrical portion other than the step has an inclination in such a manner that the inner diameter of the cylindrical portion increases toward the front end portion.

[0017] The inorganic filler (B) comprises a powdery inorganic filler (B1),

[0018] The amount of the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A).

[0019] The polyarylene sulfide resin composition has a TD / MD ratio of a tensile modulus at 150° C. of 0.7 to 1.0.

[0020] The PAS resin composition according to one embodiment of the present disclosure is characterized in that:

[0021] The invention is a PAS resin composition for forced mold release molding, which is prepared by mixing a PAS resin (A) and an inorganic filler (B).

[0022] The inorganic filler (B) comprises a powdery inorganic filler (B1),

[0023] The amount of the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A).

[0024] The PAS resin composition has a TD / MD ratio of a tensile modulus at 150° C. of 0.7 to 1.0.

[0025] The method for producing a PAS resin composition according to one embodiment of the present disclosure is characterized by comprising the following steps:

[0026] The PAS resin (A) and the inorganic filler (B) are mixed and melt-kneaded at a temperature not lower than the melting point of the PAS resin (A).

[0027] The inorganic filler (B) comprises a powdery inorganic filler (B1),

[0028] The amount of the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A).

[0029] A method for producing a forced-release molded product according to an embodiment of the present disclosure is as follows: the forced-release molded product is produced by melt molding.

[0030] The present disclosure relates to a method of using the forced-release molded product described above as a piping member that comes into contact with liquid or steam.

[0031] Effects of the Invention

[0032] According to the present disclosure, it is possible to provide a PAS forced-release molded product in which deformation of a cylindrical portion after forced-release molding is suppressed, a PAS resin composition capable of providing the molded product, and methods for producing the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a perspective view of the main parts of the forced-release molded product according to one embodiment of the present disclosure, and is a schematic view of the forced-release molded product used in the examples.

[0034] Figure 2 for Figure 1 A cross-sectional view of the main parts of a forced demolding molded product.

[0035] Figure 3 For use in Figure 1 A diagram illustrating forced demolding of a molded product. DETAILED DESCRIPTION

[0036] <Forced demolding molded products>

[0037] Hereinafter, a forced-release molded product 1 according to one 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 forced-release molded product 1 .

[0038] Figure 1 1 is a perspective view of the main part of the forced-release molded product 1 of the present embodiment. In the present embodiment, the main part of the forced-release molded product 1 includes a cylindrical part 10 having a bulging part 11 . Figure 2 for Figure 1The cross-sectional view of the forced-release molded product 1 at AA is shown. The forced-release molded product 1 is formed by injection molding a PAS resin composition and then forcedly releasing the mold during demolding. Figure 3 For use in Figure 1 FIG. 1 is a diagram for explaining forced demolding of a molded product 1. Here, forced demolding refers to a molding method in which a mold 30 is pulled axially over a bulging portion 11 of a molded product. In addition, a PAS resin composition is a composition obtained by mixing a PAS resin and a fibrous filler. The details of the PAS resin composition are described below.

[0039] In this embodiment, the cylindrical portion 10 of the forced demolding molded product 1 has a bulging portion 11 in the shape of an undercut protruding in the outer diameter direction in a portion (front end portion 16) in a certain range along the axial direction from the front end 15. Here, the cylindrical portion 10 has two circular bottom surfaces centered on the axis CA, and has a cylindrical shape in which both bottom surfaces are open. In other words, the cylindrical portion 10 has a hollow piping shape with the front end 15 and the end 17 being open. In addition, the outer diameter direction is a direction perpendicular to the direction along the axis CA, that is, the axial direction, and is a direction from the axis CA toward the side.

[0040] like Figure 1 As shown, the end 17 of the cylindrical portion 10 can be connected to other parts of the forced demolding molded product 1. That is, the end 17 of the cylindrical portion 10 is located at a position farthest from the front end 15 in the axial direction, such that the cross section is a circle centered on the axis CA. Here, the shape of the cylindrical portion 10 is symmetrical about the axis CA. For example Figure 2 The two cross sections of the cylindrical portion 10 shown are vertically symmetrical about the axis CA.

[0041] like Figure 2 As shown, the outer surface 21 of the cylindrical portion 10 extends axially from the terminal end 17 toward the front end 15 until reaching the front end portion 16. Moreover, the outer surface 21 is connected to the bulging portion 11 of the top portion 12 that protrudes most in the outer diameter direction at the front end portion 16.

[0042] The inner surface 22 of the cylindrical portion 10 has a step 13 extending in the outer diameter direction at the front end portion 16. In addition, the portion of the inner surface 22 of the cylindrical portion 10 other than the step 13 has an inclination such that the inner diameter of the cylindrical portion 10 increases as it moves from the end 17 toward the front end portion 16. In this embodiment, the inclination is constant. The portion of the inner surface 22 of the cylindrical portion 10 other than the step 13 is connected to the step 13 at the connection portion 14. Here, Figure 2 The inclined portion 18 shown is a portion having a certain inclination from the end 17 toward the front end portion 16, that is, a portion of the inner surface 22 of the cylindrical portion 10 excluding the step 13. The connecting portion 14 is located at the end of the inclined portion 18 on the front end 15 side.

[0043] like Figure 3 As shown in FIG. 1 , the cylindrical portion 10 having the bulging portion 11 is formed by forced demolding. During demolding, the mold 30 is pulled along the axial direction from the end 17 toward the front end portion 16. At this time, the force from the mold 30 is applied to the bulging portion 11, and the front end portion 16 is bent toward the axis CA side with the corner 14a at the step 13 as a fulcrum.

[0044] In this embodiment, the value of the undercut ratio is not limited. However, from the viewpoint of preventing molding defects such as breakage caused by elastic deformation of the bulge 11 during forced demolding, the undercut ratio may be preferably 20% or less, more preferably 14% or less. In addition, from the viewpoint of preventing the bulge 11 from detaching when inserted into a flexible tube or pipe, the undercut ratio may be preferably 5% or more, more preferably 3.5% or more.

[0045] Here, the undercut ratio is defined by the following formula (c).

[0046]

[0047] The outer diameter C of formula (c) is as follows Figure 2 , which is the outer diameter of the cylindrical portion 10 at the top 12 of the bulged portion 11 .

[0048] The outer diameter B of formula (c) is Figure 2 , which is the outer diameter of the cylindrical portion 10 excluding the bulged portion 11 .

[0049] The circular retention rate of the cylindrical portion 10 of the forced demolding molded product 1 of this embodiment is preferably 90% or more, more preferably 95% or more. Thus, a molded product with excellent appearance can be obtained. It should be noted that the circular retention rate is a value calculated from the value measured by a dimension measuring machine using the method described in the examples.

[0050] The arithmetic mean height Sa of the inner wall surface of the bulging portion 11 of the forced demolding molded product 1 of the present embodiment is preferably 60 [μm] or less, more preferably 50 [μm] or less. In addition, the maximum height Sz of the inner wall surface of the bulging portion 11 is preferably 350 [μm] or less, more preferably 300 [μm] or less. It should be noted that the arithmetic mean height Sa and the maximum height Sz are values ​​measured according to ISO 25178 and the method described in the examples.

[0051] <PAS resin composition>

[0052] The forced-release molded article 1 is formed of a PAS resin composition prepared by mixing a PAS resin (A) and an inorganic filler (B). The PAS resin composition described below (PAS resin composition of the present disclosure) can be used exclusively for the forced-release molded article 1 .

[0053] The PAS resin composition disclosed herein is prepared by blending a PAS resin (A) as an essential component. The PAS resin (A) has a resin structure having a structure formed by bonding an aromatic ring and a sulfur atom as a repeating unit, specifically, a resin having a structural part represented by the following general formula (1) and, if necessary, a trifunctional structural part represented by the following general formula (2) as a repeating unit.

[0054]

[0055] (In formula (1), R 1 and R 2 Each independently represents 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.

[0056]

[0057] The trifunctional structural part represented by formula (2) is preferably in the range of 0.001 to 3 mol %, particularly preferably in the range of 0.01 to 1 mol %, based on the total molar number of the trifunctional structural part and other structural parts.

[0058] Here, from the viewpoint of the mechanical strength of the PAS resin, the structural part represented by the general formula (1), especially R 1 and R 2 It is preferably a hydrogen atom, and in this case, examples thereof include a hydrogen atom bonded at the para position as shown in the following formula (3) and a hydrogen atom bonded at the meta position as shown in the following formula (4).

[0059]

[0060] Among these, in terms of heat resistance and crystallinity of the PAS resin, it is particularly preferred that the bond between the sulfur atom and the aromatic ring in the repeating unit is a structure in which the bond is at the para position as represented by the general formula (3).

[0061] The PAS resin may contain not only the structural moieties represented by the general formulae (1) and (2) but also structural moieties represented by the following structural formulae (5) to (8) in an amount of 30 mol% or less of the total of the structural moieties represented by the general formulae (1) and (2).

[0062]

[0063] In particular, in the present disclosure, it is preferred that the structural parts represented by the general formulae (5) to (8) account for 10 mol% or less from the perspective of heat resistance and mechanical strength of the PAS resin. In the aforementioned PAS resin, when the structural parts represented by the general formulae (5) to (8) are included, their bonding form may be any of a random copolymer and a block copolymer.

[0064] The PAS resin may have a naphthyl sulfide bond or the like in its molecular structure, but the proportion thereof is preferably 3 mol% or less, particularly preferably 1 mol% or less, based on the total molar number of other structural parts.

[0065] Regarding the crosslinking method of PAS resin, there can be used a method in which a low molecular weight straight-chain structure polymer obtained by condensation polymerization of monomers mainly composed of a bifunctional halogenated aromatic compound represented by the above general formula (1) is heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by crosslinking or thermal crosslinking. There can also be used a method in which a small amount of monomers such as a polyhalogenated aromatic compound having three or more halogen functional groups as represented by the above general formula (2) is used during the condensation polymerization to partially form a branched structure or a crosslinked structure.

[0066] The physical properties of the PAS resin (A) are not particularly limited unless the effects of the present invention are impaired, and are as follows.

[0067] (Melt viscosity)

[0068] The melt viscosity of the PAS resin (A) is not particularly limited. From the perspective of achieving 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 melt viscosity (V6) is measured as follows: the PAS resin is tested using a flow tester, CFT-500D, manufactured by Shimadzu Corporation, at 300°C and a load of 1.96×10 6 Pa, L / D = 10 (mm) / 1 (mm) after maintaining for 6 minutes measured melt viscosity.

[0069] (Non-Newtonian index)

[0070] The non-Newtonian index of the PAS resin (A) is not particularly limited, and is preferably in the range of 0.90 to 2.00. When a linear 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, preferably in the range of 1.50 or less, and more preferably in the range of 1.20 or less. Such a PAS resin has excellent mechanical properties, fluidity, and abrasion resistance. Among them, the non-Newtonian index (N value) is a value calculated by measuring the shear rate (SR) and the shear stress (SS) using a capillary rheometer at a melting point of +20°C and a ratio of the orifice length (L) to the orifice diameter (D) of L / D=40 and using the following formula. It shows that the closer the non-Newtonian index (N value) is to 1, the closer the structure is to linearity, and the higher the non-Newtonian index (N value), the more branched the structure is.

[0071] SR=K·SS N

[0072] [SR represents the shear rate (seconds) -1 ), SS represents shear stress (dyne / cm 2 ), and K represents a constant. ]

[0073] (Method for producing PAS resin)

[0074] The method for producing PAS resin (A) is not particularly limited, and examples thereof include the following methods: (Production method 1) a method for polymerizing a dihalogenated aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, adding a polyhalogenated aromatic compound or even other copolymerization components to polymerize; (Production method 2) a method for polymerizing a dihalogenated aromatic compound in a polar solvent in the presence of a thioetherifying agent, and if necessary, adding a polyhalogenated aromatic compound or even other copolymerization components to polymerize; (Production method 3) a method for self-polymerizing p-chlorothiophenol and, if necessary, adding other copolymerization components to self-condense; (Production method 4) a method for melt-polymerizing a diiodide aromatic compound and elemental sulfur while reducing pressure in the presence of a polymerization inhibitor optionally having functional groups such as carboxyl groups and amino groups; etc. Among these methods, the method of (Production method 2) is general and preferred. During the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid, or an alkali metal hydroxide may also be added to adjust the degree of polymerization. Among the above-mentioned methods (production method 2), a method for producing a PAS resin by introducing a water-containing thioetherification agent into a mixture containing a heated organic polar solvent and a dihalogenated aromatic compound at a rate at which water can be removed from the reaction mixture, reacting the dihalogenated aromatic compound and the thioetherification agent in the organic polar solvent, adding a polyhalogenated aromatic compound as needed, and controlling the amount of water in the reaction system to be in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent (see Japanese Patent Application Laid-Open No. 07-2286-1999) is particularly preferred. 99 Communiqué. ); In the presence of a solid alkali metal sulfide and a non-protonic polar organic solvent, a dihalogenated aromatic compound, if necessary, a polyhalogenated aromatic compound or even other copolymerization components are added, while the amount of the organic acid alkali metal salt is controlled to be in the range of 0.01 to 0.9 mol relative to 1 mol of the sulfur source and the amount of water in the reaction system is controlled to be in the range of 0.02 mol or less relative to 1 mol of the non-protonic polar organic solvent, and the alkali metal hydrosulfide and the organic acid alkali metal salt are reacted (see WO2010 / 058713 pamphlet.).Specific examples of the dihalogenated 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, and 4,4'-dihalobenzophenone. , 4,4'-dihalogenodiphenyl sulfone, 4,4'-dihalogenodiphenyl sulfoxide, 4,4'-dihalogenodiphenyl sulfide, and compounds having an alkyl group with a carbon number of 1 to 18 on the aromatic ring of each of the above compounds. As polyhalogenated aromatic compounds, 1,2,3-trihalogenobenzene, 1,2,4-trihalogenobenzene, 1,3,5-trihalogenobenzene, 1,2,3,5-tetrahalogenobenzene, 1,2,4,5-tetrahalogenobenzene, 1,4,6-trihalonaphthalene, etc. can be cited. In addition, the halogen atoms contained in each of the above compounds are preferably chlorine atoms or bromine atoms.

[0075] The post-treatment method of the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited, and examples thereof include the following methods: (Post-treatment 1) After the polymerization reaction is completed, first, the reaction mixture is directly or after adding an acid or a base, and the solvent is distilled off under reduced pressure or normal pressure, and then the solid matter after the solvent is distilled off is washed once or twice or more with a solvent such as water, a reaction solvent (or an organic solvent having an equivalent solubility to the low molecular weight polymer), acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered and dried; or (Post-treatment 2) After the polymerization reaction is completed, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, etc. (a solvent soluble in the polymerization solvent used and at least a poor solvent for PAS) is added to the reaction mixture as a precipitant, so that A method in which solid products such as PAS and inorganic salts are precipitated, and they are filtered, washed with water, and dried; or, (post-treatment 3) after the polymerization reaction is completed, a reaction solvent (or an organic solvent having an equivalent solubility to the low-molecular-weight polymer) is added to the reaction mixture and stirred, and then the low-molecular-weight polymer is removed by filtering, and then the reaction mixture is washed once or twice with solvents such as water, acetone, methyl ethyl ketone, and alcohols, and then the reaction mixture is neutralized, washed with water, filtered, and dried; (post-treatment 4) after the polymerization reaction is completed, water is added to the reaction mixture, washed with water, filtered, and an acid or base is added during the water washing as needed, and the reaction mixture is treated and dried; (post-treatment 5) after the polymerization reaction is completed, the reaction mixture is filtered, washed with a reaction solvent once or twice as needed, and then washed with water, filtered, and dried. In any post-treatment method, acid or alkali is added to adjust the pH during the water washing step to control the reactivity, crystallization rate, sodium content, etc. of the PAS resin. The pH after the hot water washing step can be controlled so that it is in the range of 6.5 to 11.5, more preferably in the range of 6.5 to 8.5.

[0076] In the post-treatment methods exemplified in (Post-treatment 1) to (Post-treatment 5) above, the drying of the PAS resin may be performed in a vacuum or in an inert gas atmosphere such as air or nitrogen.

[0077] The PAS resin (A) used in the present embodiment may be a PAS resin repolymerized by the above method, or a PAS resin recycled. 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 as follows may be cited: a PAS resin obtained by subjecting a PAS resin composition or a PAS resin molded product to the above-mentioned post-treatment of a solution obtained by heating the PAS resin composition or the PAS resin molded product in an organic polar solvent to dissolve the PAS contained therein. In addition, a PAS resin composition or a PAS resin molded product that is mechanically crushed may be used as a PAS resin. Specifically, a sprue or runner generated when manufacturing a molded product, a molded product recovered as a non-standard molded product, a molded product used as a disposable product, etc. may be cited. In this case, a crushed product of a PAS resin composition or a PAS resin molded product containing components other than the PAS resin may also be cited.

[0078] <Inorganic filler (B)>

[0079] The PAS resin composition of the present disclosure is blended with an inorganic filler (B). The inorganic filler (B) contains a powdery inorganic filler (B1) as an essential component. Furthermore, a plate-like inorganic filler (B2) and a fibrous inorganic filler (B3) may be used as optional components.

[0080] As the raw material of the inorganic filler (B) applicable to the present disclosure, those known in the art can be used, and the fiber diameter, fiber length, aspect ratio, etc. thereof can be appropriately adjusted according to the application of the molded article, etc.

[0081] The inorganic filler (B) that can be used in the present disclosure can also be processed with a surface treatment agent or a sizing agent. In this way, the adhesion with the PAS resin (A) can be improved, so it is preferred. As the aforementioned surface treatment agent or sizing agent, for example, at least one polymer selected from the group consisting of silane compounds, titanate compounds, acrylic resins, carbamate resins, polyether resins and epoxy resins having functional groups such as amino groups, epoxy groups, isocyanate groups, and vinyl groups can be cited. From the viewpoint of suppressing excessive defibration during processing, it is particularly preferred to contain a carbamate resin. In the case where the aforementioned surface treatment agent or sizing agent contains a carbamate resin, there is no particular limitation on its content. From the viewpoint of resistance to fuel swelling, the range of less than 35% by mass is preferred, and the range of less than 20% by mass is more preferred.

[0082] The amount of the inorganic filler (B) is preferably 40 parts by volume or more, more preferably 50 parts by volume or more, and further preferably 60 parts by volume or more relative to 100 parts by volume of the PAS resin (A) from the viewpoint of obtaining a more excellent mechanical strength. On the other hand, from the viewpoint of the fluidity and processability of the resin composition, it is preferably 180 parts by volume or less, more preferably 140 parts by volume or less, and further preferably 90 parts by volume or less.

[0083] As the powdery inorganic filler (B1) applicable in the present disclosure, known and commonly used materials can be used, for example, fillers of various shapes such as plate-like and powdery ones can be cited. Specifically, silicates such as graphite, silicon dioxide, quartz powder, glass beads, calcium silicate, aluminum silicate, diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, aluminum oxide, metal carbonates such as calcium carbonate, magnesium carbonate, metal sulfates such as calcium sulfate, barium sulfate, and silicon carbide, silicon nitride, boron nitride, various metal powders, etc. can be cited, and one or more kinds can be appropriately selected according to the required performance. Among them, calcium carbonate and glass beads can be preferably used.

[0084] The average particle size (D 50 ) 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, further preferably in the range of 20 μm or less, and particularly preferably in the range of 2 μm or less. It should be noted that the average particle size is an average particle size (D) obtained based on the particle size distribution measured by a laser diffraction scattering particle size distribution measuring machine (Microtrac MT3300EXII) according to a conventional method. 50 ).

[0085] The amount of the powdery inorganic filler (B1) in the PAS resin composition of the present invention is not particularly limited unless the effects of the present invention are impaired, but is preferably in the range of 15 parts by volume or more, more preferably 30 parts by volume or more, and further preferably 40 parts by volume or more, to preferably 180 parts by volume or less, more preferably 140 parts by volume or less, and further preferably 90 parts by volume or less, relative to 100 parts by volume of the PAS resin (A). Within the above range, the resin composition has good fuel swelling resistance and moldability, particularly mold release properties, and the molded product exhibits high dimensional accuracy, which is preferred.

[0086] As the plate-like inorganic filler (B2) applicable in the present disclosure, known and commonly used materials can be used, for example, glass flakes, talc, mica, kaolin, clay, alumina, various metal foils, etc., and one or more kinds can be appropriately selected according to the required performance. Among these, glass flakes are preferably used from the viewpoint of mechanical strength and ease of operation.

[0087] The amount of the plate-like inorganic filler (B2) in the PAS resin composition disclosed herein is not particularly limited as long as the effects of the present invention are not impaired, but is preferably within the range of 80 parts by volume or less, more preferably 50 parts by volume or less, and further preferably 10 parts by volume or less, relative to 100 parts by volume of the above-mentioned powdery inorganic filler (B1). Within the above range, the resin composition has good fuel swelling resistance and moldability, especially demolding properties, and the molded product exhibits high dimensional accuracy, which is preferred.

[0088] As the fibrous inorganic filler (B3) that can be used in the present disclosure, known and commonly used materials can be used, for example, glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconium oxide fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite, and metal fiber-like substances such as stainless steel, aluminum, titanium, copper, and brass can be cited, and one or more kinds can be appropriately selected according to the required performance. Among these, from the viewpoint of mechanical strength and ease of operation, glass fiber is preferably used.

[0089] The amount of the fibrous inorganic filler (B3) in the PAS resin composition disclosed herein is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 230 parts by volume or less, more preferably 130 parts by volume or less, further preferably 100 parts by volume or less, and particularly preferably 20 parts by volume or less, relative to 100 parts by volume of the above-mentioned particulate inorganic filler (B1). Within the above range, the resin composition has good fuel swelling resistance and moldability, especially demolding properties, and the molded product exhibits high dimensional accuracy, which is preferred.

[0090] The PAS resin composition disclosed in the present invention may be blended with a silane coupling agent as an optional component as needed. As the silane coupling agent, there is no particular limitation as long as the effect of the present invention is not impaired, and a silane coupling agent having a functional group reactive with a carboxyl group, such as an epoxy group, an isocyanate group, an amino group or a hydroxyl group may be cited as a preferred example. As such a silane coupling agent, for example, epoxy-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylethyl Alkoxysilane compounds containing cyanate groups such as dimethoxysilane, γ-isocyanate propyl ethyl diethoxysilane, γ-isocyanate propyl trichlorosilane, γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane, γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, hydroxyl-containing alkoxysilane compounds such as γ-hydroxypropyl trimethoxysilane, γ-hydroxypropyl triethoxysilane. In the present disclosure, the silane coupling agent is not a necessary component. In the case of blending, the amount of blending is not particularly limited to its addition amount as long as it does not damage the effect of the present invention. With respect to 100 parts by mass of PAS resin (A), preferably 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. Within the above range, the resin composition has good moldability, especially demoulding properties, and the mechanical strength of the molded product is improved, so it is preferred.

[0091] The PAS resin composition disclosed herein can be blended with a thermoplastic elastomer as an arbitrary component as needed. As a thermoplastic elastomer, a polyolefin elastomer, a fluorine-based elastomer or a silicone-based elastomer can be cited, wherein a polyolefin elastomer can be cited as a preferred example. When these elastomers are added, the amount thereof is not particularly limited as long as it does not impair the effect 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 PAS resin (A). Within the above range, the impact resistance of the obtained PAS resin composition is improved, so it is preferred.

[0092] For example, the polyolefin elastomer may include: a homopolymer of α-olefin; or 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 ethylene, propylene, 1-butene, and other α-olefins having a carbon number ranging from 2 to 8. In addition, examples of the functional group include a carboxyl group, an acid anhydride group (-C(=O)OC(=O)-), an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, an oxazoline group, and the like. Furthermore, examples of the vinyl polymerizable compound having a functional group include: 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 are 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 anhydrides) of the above-mentioned α,β-unsaturated dicarboxylic acids, or one or more of the above-mentioned thermoplastic elastomers. The above-mentioned thermoplastic elastomers may be used alone or in combination of two or more.

[0093] Furthermore, in the PAS resin composition of the present disclosure, in addition to the above-mentioned components, 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, polyvinylidene fluoride resin, polystyrene resin, ABS resin, phenolic resin, urethane resin, liquid crystal polymer and other synthetic resins (hereinafter referred to as synthetic resins) may be appropriately blended as an arbitrary component according to the application. In the present disclosure, the above-mentioned synthetic resin is not an essential component, and when blended, the blending ratio thereof is not particularly limited as long as the effect of the present invention is not impaired. In addition, it varies according to each purpose and cannot be generalized. As the ratio of the synthetic resin blended in the resin composition of the present disclosure, for example, the range of 5 parts by mass or more and 15 parts by mass or less can be cited with respect to 100 parts by mass of the 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.

[0094] In addition, the PAS resin composition of the present disclosure may also contain, as required, known and commonly used additives such as colorants, antistatic agents, antioxidants, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, foaming agents, flame retardants, flame retardant aids, rust inhibitors, and mold release agents (including metal salts and esters of fatty acids having 18 to 30 carbon atoms such as stearic acid and montanic acid, polyethylene and other polyolefin waxes, etc.) as arbitrary components. These additives are not essential components, and, for example, in order not to impair the effects of the present invention, they may be used in an amount preferably in the range of 0.01 parts by mass or more, preferably in the range of 100 parts by mass or less, more preferably in the range of 100 parts by mass or less, and further preferably in the range of 10 parts by mass or less, and appropriately adjusted according to the purpose and application.

[0095] 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. Within the above range, the deformation of the molded product before and after the forced demolding process in the molding process can be suppressed, and the dimensional accuracy is excellent. In order to make the PAS resin composition have the above properties, it is effective to adjust the compounding amount of the inorganic filler (B), for example, it can be achieved by adjusting the amount of the granular inorganic filler (B1) as an essential component, the plate-like inorganic filler (B2) as an optional component, and the fibrous inorganic filler (B3). It should be noted that the TD / MD ratio of the tensile modulus at 150°C in the present disclosure is a value measured according to the method of the embodiment. It should be noted that in the present disclosure, MD refers to the flow direction of the resin during molding, and refers to the direction in which the fiber orientation parameter is greater than 0.9. On the other hand, TD refers to the direction orthogonal to the flow direction of the resin during molding, and refers to the direction in which the fiber orientation parameter is less than 0.1. The closer the TD / MD ratio is to 1, the smaller the anisotropy of the elastic modulus.

[0096] The tensile modulus of the PAS resin composition disclosed in the present invention at room temperature (23°C) is not particularly limited, but is preferably 15 [GPa] or less, and more preferably 8 [GPa] or less. Within the above range, the deformation of the molded product before and after the forced demolding process in the molding process can be suppressed, and the dimensional accuracy is excellent, so it is preferred. It should be noted that the tensile modulus in the present invention is a value measured using an ISO Type-A dumbbell obtained by injection molding the PAS resin composition in accordance with the method of ISO 527-1 and 2.

[0097] The method for producing a PAS resin composition disclosed herein is characterized in that it comprises the following steps: blending a PAS resin (A) and an inorganic filler (B) as essential components, and melt-kneading them in a temperature range above the melting point of the PAS resin (A), wherein the inorganic filler (B) comprises a powdery inorganic filler (B1), and the powdery inorganic filler (B1) is 15 to 180 parts by volume relative to 100 parts by volume of the PAS resin (A). This is described in detail below.

[0098] The method for producing the PAS resin composition of the present disclosure comprises the following steps: blending the above-mentioned essential components and melt-kneading them in a temperature range above the melting point of the PAS resin (A). In more detail, the PAS resin composition of the present disclosure is formed by blending the essential components and other optional components as required. There is no particular limitation on the method for producing the resin composition applicable to the present disclosure, and a method of blending the essential components and the optional components as required and melt-kneading them can be cited. In more detail, the following method can be cited: uniformly dry-mixing in a drum or a Henschel mixer as required, and then, feeding into a twin-screw extruder for melt-kneading.

[0099] Melt kneading can be carried out by heating the resin temperature to a temperature range of not less than the melting point of the PAS resin (A), preferably not less than the melting point + 10°C, more preferably not less than the melting point + 10°C, further preferably not less than the melting point + 20°C, preferably not more than the melting point + 100°C, more preferably not more than the melting point + 50°C.

[0100] As the aforementioned melt kneader, from the viewpoint of dispersibility and productivity, a twin-screw kneading extruder is preferred. For example, it is preferred to perform melt kneading while appropriately adjusting the ejection amount of the resin component in the range of 5 to 500 (kg / hr) and the screw speed in the range of 50 to 500 (rpm), and it is further preferred to perform melt kneading under the condition that their ratio (ejection amount / screw speed) reaches the range of 0.02 to 5 (kg / hr / rpm). In addition, the addition and mixing of each component to the melt kneader can be carried out simultaneously or in batches. For example, when adding the inorganic filler (B) which is a necessary component of the aforementioned components, it can also be fed into the extruder from the side feeder of the aforementioned twin-screw kneading extruder. Regarding the position of the side feeder, the ratio of the distance from the extruder resin input part (top feeder) to the side feeder relative to the total length of the screw of the aforementioned twin-screw kneading extruder is preferably 0.1 or more, more preferably 0.3 or more. In addition, the ratio is preferably 0.9 or less, more preferably 0.7 or less.

[0101] The PAS resin composition of the present invention obtained by melt kneading in this way is a molten mixture containing the aforementioned essential components, as well as optional components added as needed and components derived from these. Therefore, the PAS resin composition of the present invention has a form in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. The PAS resin composition of the present invention is preferably subjected to a known method after the melt kneading, for example, after the resin composition in a molten state is extruded into a strand shape, it is processed into a form such as pellets, flakes, granules, powder, etc., and then pre-dried in a temperature range of 100 to 150° C. as needed.

[0102] The molded product disclosed herein is formed by melt-molding a PAS resin composition. In addition, the method for manufacturing the molded product disclosed herein comprises a step of melt-molding the aforementioned PAS resin composition. Therefore, the molded product disclosed herein has a form in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. The PAS resin composition has the above-mentioned form to obtain a molded product having excellent fuel swelling resistance and mechanical strength.

[0103] The PAS resin composition disclosed in the present invention can be used for various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., drawing molding, blow molding, transfer molding, etc., and has excellent demolding properties. Therefore, it is particularly suitable for injection molding. In the case of molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by general methods. For example, in an injection molding machine, after the resin temperature is melted in a temperature range above the melting point of the PAS resin (A), preferably in a temperature range above the melting point + 10°C, more preferably in a temperature range of melting point + 10°C to melting point + 100°C, and further preferably in a temperature range of melting point + 20 to melting point + 50°C, the PAS resin composition is injected into the mold from the resin outlet and molded. At this time, the mold temperature is also set to a known temperature range, such as room temperature (23°C) to 300°C, preferably 130 to 190°C.

[0104] The manufacturing method of the PAS resin molded product disclosed in the present invention comprises a step of annealing the aforementioned molded product. The annealing treatment selects the best conditions according to the purpose or shape of the molded product, and the annealing temperature is preferably in the range of 100°C or above, and more preferably in the range of 120°C or above. On the other hand, the range of 260°C or below, and more preferably in the range of 240°C or below is preferred. The annealing time is not particularly limited, and is preferably in the range of 0.5 hours or above, and more preferably in the range of 1 hour or above. On the other hand, the range of 10 hours or below, and more preferably in the range of 8 hours or below is preferred. Within the above range, the strain of the obtained molded product is reduced, and the crystallinity of the resin is improved, so it is preferred. The annealing treatment can be carried out in air, but is preferably carried out in an inert gas such as nitrogen.

[0105] The molded product of the present embodiment includes: a re-molded product obtained by reusing a molded product formed by melt-molding the aforementioned PAS resin composition. Specifically, for example, it includes a molded product obtained as follows: a sprue or runner generated when manufacturing a molded product, a molded product recovered as a non-standard molded product, and a molded product used as a disposable product are cleaned as needed, crushed, and melt-molded again at a temperature above the melting point of the PAS resin. When reused, from the viewpoint of mechanical properties, it is preferred to mix the crushed molded product with the aforementioned PAS resin composition for use. The size of the crushed molded product is not particularly limited, and from the viewpoint of miscibility and processability, it is preferably the same size as the aforementioned PAS resin composition to be mixed. In addition, for the mixing ratio, the crushed product of the molded product is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less relative to 100 parts by mass of the PAS resin composition. Within the above range, the recyclability can be improved without impairing the effect presented by the PAS resin composition disclosed herein.

[0106] The PAS resin molded product disclosed in the present invention is characterized in that it has excellent forced demolding properties and is therefore particularly suitable for parts made using a forced demolding mold. Examples include piping, containers, joints, valve bodies, and more specifically, various parts that come into contact with liquid or steam, such as pipes, liner pipes, cap nuts, pipe joints (elbows, headers, manifolds, reducers, joints, couplers, etc.), various valves, flow meters, gaskets (seals, liners), and the like. In addition, the molded product disclosed in the present invention can also be formed into a conventional resin molded product such as the following.Examples include box-shaped protection / support members for electrical / electronic component integrated modules / multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay boxes, switches, coil skeletons, capacitors, variable capacitor boxes, optical pickups, vibrators, various terminal boards, converters, plugs, printed circuit boards, tuners, loudspeakers, microphones, earphones, small motors, head supports, etc. Electric / electronic components represented by VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, audio / optical discs / compact discs / DVD discs / Blu-ray discs and other audio / visual equipment components, lighting components, refrigerator components, air conditioning components, typewriter components, word processor components, or water heaters, bath water volume, temperature sensors and other water-related equipment components, etc.; Mechanical components represented by office computer components, telephone components, fax components, copier components, cleaning tools, motor components, igniters, typewriters, etc.; Optical equipment and precision machinery components represented by microscopes, binoculars, cameras, watches, etc.; AC generator terminals, AC generator connectors, brush holders, slip rings, IC regulators, dimmer variable resistor bases, relay modules, etc. block, inhibitor switch, exhaust valve and other valves; various pipelines related to fuel / exhaust system / intake system, intake nozzle connecting pipe, intake manifold, engine cooling water joint, carburetor body, carburetor partition, exhaust sensor, cooling water sensor, oil temperature sensor, brake lining wear sensor, throttle position sensor, crankshaft position sensor, temperature sensor, air flow meter, brake lining wear sensor, air conditioner thermostat base, heater hot air flow control valve, radiator motor brush holder, water Pump impellers, turbine blades, wiper motor related parts, distributors, starter switches, ignition coils and their coil frames, motor insulators, motor rotors, motor cores, starter relays, transmission harnesses, windshield washer nozzles, air conditioning panel switch substrates, fuel-related solenoid valve coils, fuse connectors, speaker terminals, electrical component insulation boards, stepper motor rotors, lamp holders, lamp reflectors, lamp covers, brake pistons, solenoid coil bobbins, engine oil filters, ignition device housings and other automobile / vehicle related parts, and can also be used for various other purposes.

[0107] Example

[0108] Hereinafter, the present invention will be described using Examples and Comparative Examples, but the present invention is not limited to these Examples. It should be noted that "%" and "parts" are based on volume unless otherwise specified.

[0109] <Examples 1 to 7 and Comparative Examples 1 to 4>

[0110] The materials were mixed according to the composition and compounding amount described in Tables 1 and 2. Thereafter, these compounding materials were put into a twin-screw extruder "TEX-30α (product name)" with ventilation holes manufactured by Nippon Steel Works, Ltd., and melt-kneaded under the conditions of a resin component ejection 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. Glass fiber was fed from a side feeder (S / T ratio 0.5), and other materials were pre-mixed uniformly using a rotating drum and fed from a top feeder. The pellets of the obtained resin composition were dried in a Gill aging thermostat at 140°C for 2 hours, and then injection molded to produce various test pieces, and the following tests were carried out.

[0111] <Evaluation>

[0112] (1) Evaluation of tensile properties

[0113] The obtained pellets were supplied to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with the barrel temperature set at 310°C, and injection molded with an ISO Type-A dumbbell molding mold with the mold temperature adjusted to 140°C to obtain an ISO Type-A dumbbell. It should be noted that the test piece was made by injecting resin from a single gate in such a way that it did not contain a welded portion. For the obtained dumbbell, the tensile modulus and tensile elongation at break were measured at room temperature according to the measurement method based on ISO 527-1 and 2. The results are shown in Tables 1 and 2.

[0114] (2) Measurement of TD / MD ratio of tensile modulus at 150°C

[0115] Under the same conditions as (1), injection molding was performed using a molding mold of 100×100×2 mm2 to obtain a sheet-shaped molded product. Using the obtained molded product, a dumbbell (ISO Type 1BA) for tensile testing was cut in the flow direction of the resin (MD direction) and in the direction orthogonal to the MD direction (TD direction). For the obtained dumbbell sheet, the tensile modulus at 150°C was measured according to the 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.

[0116] (3) Determination of surface roughness (Sa and Sz) of forced demolding molded products

[0117] The obtained pellets were supplied to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a barrel temperature set to 310°C, and injection molding was performed using a mold with a forced demolding structure with a mold temperature adjusted to 140°C to obtain a molded product in the shape of a pipe (inner diameter φ11.5, undercut ratio 15). The presence or absence of cracks on the inner diameter side surface of the front end of the pipe was visually confirmed. If cracks were present, the surface roughness (arithmetic mean height Sa and maximum height Sz) of the portion was measured using a 3D dimension measuring machine ("VR-5200" manufactured by KEYENCE CORPORATION) in accordance with ISO 25178. In the case of large and deep cracks, Sa and Sz showed larger values. The results are shown in Tables 1 and 2.

[0118] (4) Evaluation of the roundness retention rate of forced demolding molded products

[0119] The evaluation was performed using a molded product of the same pipe shape as in (3). The outer diameter dimension from the front end of the cylinder to the top of the bulge was measured at the location (a) where the inner diameter of the pipe tip had the largest tilt and the location (b) where the tilt was the smallest. Figure 2 The dimension from the front end 15 of the cylindrical part 10 to the top 12 of the bulging part 11 in the figure). The roundness is calculated from the measured value according to 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.

[0120] Roundness retention rate (%) = (b) size (mm) / (a) size (mm) × 100

[0121] [Table 1]

[0122]

[0123] [Table 2]

[0124]

[0125] ·PAS resin (A)

[0126] PPS resin

[0127] A-1: Linear, melt viscosity (V6) 40 Pa·s, non-Newtonian index 1.16

[0128] Inorganic filler (B)

[0129] B-1: Powdered inorganic filler, glass beads, UB-02EG manufactured by Union Corporation, particle size (D 50 )19.5μm

[0130] B-2: Powdered inorganic filler, calcium carbonate, grade 1 calcium carbonate manufactured by Sankyo Seipen Co., Ltd., particle size (D 50 )1.7μm

[0131] B-3: Plate-shaped inorganic filler, glass flakes, REFG-301 manufactured by Nippon Sheet Glass Co., Ltd., base flake average particle size 160 μm, thickness 5 μm

[0132] B-4: Fibrous inorganic filler, glass fiber, ECS03T-725H manufactured by Nippon Electric Glass Co., Ltd., fiber diameter: 10 μm, fiber length: 3 mm chopped fibers

[0133] Other ingredients

[0134] C-1: Elastomer: Bondfast 7L manufactured by Sumitomo Chemical Co., Ltd.

[0135] As shown in Tables 1 and 2, the molded products of Examples have smaller surface roughness and greater roundness retention than the molded products of Comparative Examples, and thus deformation during forced demolding is suppressed.

[0136] Description of Reference Numerals

[0137] 1. Forced demoulding of molded products

[0138] 10 Cylinder

[0139] 11. Protrusion

[0140] 12 Top

[0141] 13 steps

[0142] 14 Connection

[0143] 14a Corner

[0144] 15 Frontend

[0145] 16 Front-end

[0146] 17 End

[0147] 18 Inclined part

[0148] 21 External surface

[0149] 22 Inner surface

[0150] 30 Mould

Claims

1. A forced demoulding molded product, characterized in that: In the forced mold release molded article, a polyarylene sulfide resin composition prepared by mixing a polyarylene sulfide resin (A) and an inorganic filler (B) is formed into a cylindrical portion. The cylindrical portion has a bulging portion in an undercut shape protruding in the outer diameter direction at the front end portion. The inner surface of the cylindrical portion has a step in the outer diameter direction at the front end portion, and the portion of the inner surface of the cylindrical portion other than the step has an inclination such that the inner diameter of the cylindrical portion increases toward the front end portion. The inorganic filler (B) comprises a powdery inorganic filler (B1), The powdery inorganic filler (B1) is present in an amount of 15 to 180 parts by volume relative to 100 parts by volume of the polyarylene sulfide resin (A). The polyarylene sulfide resin composition has a TD / MD ratio of a tensile modulus at 150° C. of 0.7 to 1.

0.

2. The forced demoulding molded product according to claim 1, characterized in that: The inorganic filler (B) further comprises at least a plate-like inorganic filler (B2), The amount of the plate-like inorganic filler (B2) is within a range of 60 parts by volume or less relative to 100 parts by volume of the powdery particulate inorganic filler (B1).

3. The forced demoulding molded product according to claim 1 or 2, characterized in that: The inorganic filler (B) further comprises at least a fibrous inorganic filler (B3), The amount of the fibrous inorganic filler (B3) is in a range of 230 parts by volume or less relative to 100 parts by volume of the particulate inorganic filler (B1).

4. The forced demolding molded product according to claim 1 or 2, wherein: The circularity retention rate of the cylindrical portion is 90% or more, wherein the circularity retention rate is a value obtained by measuring the outer diameter direction of the cylindrical portion from the front end portion of the cylindrical portion to the top of the bulging portion at the portion (a) where the inner diameter side tilting amount of the cylindrical portion is the largest and the portion (b) where the inner diameter side tilting amount is the smallest using a dimension measuring machine, and calculating the value according to the following formula: Circularity retention rate (%) = (b) dimension (mm) / (a) dimension (mm) × 100.

5. The forced demolding molded product according to claim 1 or 2, wherein: The arithmetic mean height Sa of the inner wall of the bulge measured by a dimension measuring machine is within the range of 60 [μm] or less and the maximum height Sz is within the range of 350 [μm] or less.

6. A polyarylene sulfide resin composition for forced demolding, characterized in that: The invention is a polyarylene sulfide resin composition for forced mold release molding, which is prepared by mixing a polyarylene sulfide resin (A) and an inorganic filler (B). The inorganic filler (B) comprises a powdery inorganic filler (B1), The powdery inorganic filler (B1) is present in an amount of 15 to 180 parts by volume relative to 100 parts by volume of the polyarylene sulfide resin (A). The polyarylene sulfide resin composition has a TD / MD ratio of a tensile modulus at 150° C. of 0.7 to 1.

0.

7. The polyarylene sulfide resin composition for forced demolding according to claim 6, characterized in that: The inorganic filler (B) further comprises a plate-like inorganic filler (B2), The amount of the plate-like inorganic filler (B2) is within a range of 60 parts by volume or less relative to 100 parts by volume of the powdery particulate inorganic filler (B1).

8. The polyarylene sulfide resin composition for forced demolding according to claim 6 or 7, characterized in that: The inorganic filler (B) further comprises a fibrous inorganic filler (B3), The amount of the fibrous inorganic filler (B3) is in a range of 230 parts by volume or less relative to 100 parts by volume of the particulate inorganic filler (B1).

9. The polyarylene sulfide resin composition for forced mold release molding according to claim 6 or 7, wherein The polyarylene sulfide resin composition is a melt-kneaded product.

10. A method for producing a polyarylene sulfide resin composition for forced demolding, characterized in that: The method comprises the steps of mixing a polyarylene sulfide resin (A) and an inorganic filler (B) and performing melt kneading at a temperature range not lower than the melting point of the polyarylene sulfide resin (A); The inorganic filler (B) comprises a powdery inorganic filler (B1), The powdery particulate inorganic filler (B1) is contained in an amount of 15 to 180 parts by volume based on 100 parts by volume of the polyarylene sulfide resin (A).

11. The method for producing a polyarylene sulfide resin composition for forced demolding according to claim 10, characterized in that: The inorganic filler (B) further comprises a plate-like inorganic filler (B2), The amount of the plate-like inorganic filler (B2) is within a range of 60 parts by volume or less relative to 100 parts by volume of the powdery particulate inorganic filler (B1).

12. The method for producing a polyarylene sulfide resin composition for forced demolding according to claim 10 or 11, characterized in that: The inorganic filler (B) further comprises a fibrous inorganic filler (B3), The amount of the fibrous inorganic filler (B3) is in a range of 230 parts by volume or less relative to 100 parts by volume of the particulate inorganic filler (B1).

13. A method for manufacturing a forced demoulding molded product, characterized in that: The method comprises the steps of: producing a polyarylene sulfide resin composition by the method according to claim 10 or 11; and performing injection molding using a mold having a forced mold release structure.

14. A method of using the forced demolding molded article according to claim 1 or 2 as a member in contact with liquid or vapor.

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