Polyphenylene Sulfide Resin Composition, Molded Article, and Methods for Producing the Same

Abstract

Provided are a molded article containing a polyarylene sulfide (PAS) resin and glass fiber and capable of suppressing a reduction in mechanical strength even in a hot water atmosphere and under acidic conditions, a PAS resin composition capable of providing the molded article, and methods for producing them. More specifically, a PAS resin composition, a molded article, and methods for producing them, which are prepared by compounding, as essential components, 10 to 100 parts by mass of glass fiber and 0.01 to 10 parts by mass of a silane coupling agent relative to 100 parts by mass of the PAS resin; in the glass fiber, MgO, CaO, and R2O are contained in a ratio such that the MgO content is 6% by mass or more, the CaO content is 16% by mass or less, and the R2O content is 1% by mass or less (wherein the R2O content represents the total content of Li2O, Na2O, and K2O).

Description

Technical Field

[0001] The present invention relates to a polyarylene sulfide resin composition, a polyarylene sulfide resin molded article, and methods for producing them. Background Art

[0002] Polyarylene sulfide resins (hereinafter "PAS resins") represented by polyphenylene sulfide resin (hereinafter "PPS resin") are excellent in heat resistance, chemical resistance, etc., and are widely used in applications such as automotive parts, electrical and electronic parts, and water heater parts. In these applications, mechanical strength to replace metals is mostly required, and they are used in the form of resin compositions reinforced with glass fibers. However, although the PPS resin itself exhibits excellent heat and chemical resistance, in applications where it comes into contact with hot water, acidic or alkaline chemicals, the strength of the resin composition decreases significantly, and its use is restricted.

[0003] For this reason, there have been provided PPS resin compositions compounded with glass fibers containing 5 to 40 wt% ZrO2 as glass excellent in acid resistance and alkali resistance (see Patent Document 1); PPS resin compositions compounded with glass fibers having a content rate of B2O3 of 1 wt% or less in order to improve water resistance (see Patent Document 2).

[0004] It is known that by further adding a polysiloxane compound to a PPS resin composition containing a PPS resin and glass fibers, acid resistance and alkali resistance can be improved without impairing water resistance (see Patent Document 3).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Laid-Open No. 10-7907

[0008] Patent Document 2: Japanese Patent Laid-Open No. 10-279800

[0009] Patent Document 3: Japanese Patent Laid-Open No. 2001-115020 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, since these methods use glass fibers with a large amount of alkali components, the reduction in mechanical strength in a hot water atmosphere and under acidic conditions is significant; in the case of containing a polysiloxane compound, durability is reduced due to its elution.

[0012] Therefore, the problem to be solved by the present invention is to provide: a molded article containing a PAS resin and glass fibers and capable of suppressing a decrease in mechanical strength even in a hot water atmosphere and under acidic conditions, a PAS resin composition capable of providing the molded article, and methods for producing them.

[0013] Solutions for Solving the Problems

[0014] In order to solve the above problems, the inventors of the present invention conducted in-depth research and found that: by using glass fibers containing specific components, it is possible to suppress the reduction of the mechanical strength of a PAS resin molded product containing a PAS resin and glass fibers in a hot water atmosphere and under acidic conditions, thereby completing the present invention.

[0015] That is, the present invention relates to a polyarylene sulfide resin composition, which is characterized in that it is a polyarylene sulfide resin composition prepared by compounding a polyarylene sulfide resin (A), glass fibers (B), and a silane coupling agent (C) as essential components.

[0016] Among them, the glass fibers (B) are glass fibers containing MgO, CaO, and R2O (where the content of R2O represents the total content of Li2O, Na2O, and K2O) in a proportion of 6% by mass or more of MgO content, 16% by mass or less of CaO content, and 1% by mass or less of R2O content in the glass fibers.

[0017] Relative to 100 parts by mass of the polyarylene sulfide resin (A), the glass fibers (B) are in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass.

[0018] In addition, the present invention relates to a molded product formed by molding the above-described polyarylene sulfide resin composition.

[0019] In addition, the present invention relates to a method for manufacturing a polyarylene sulfide resin composition, which is characterized in that it has a step of compounding a polyarylene sulfide resin (A), glass fibers (B), and a silane coupling agent (C) as essential components and performing melt-kneading in a temperature range above the melting point of the polyarylene sulfide resin (A).

[0020] Among them, the glass fibers (B) are glass fibers containing MgO, CaO, and R2O (where the content of R2O represents the total content of Li2O, Na2O, and K2O) in a proportion of 6% by mass or more of MgO content, 16% by mass or less of CaO content, and 1% by mass or less of R2O content in the glass fibers.

[0021] Relative to 100 parts by mass of the polyarylene sulfide resin (A), the glass fibers (B) are in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass.

[0022] In addition, the present invention also relates to a method for manufacturing a molded product, which has a step of manufacturing a polyarylene sulfide resin composition by the above-described manufacturing method; and a step of melt-molding the obtained polyarylene sulfide resin composition.

[0023] Effects of the Invention

[0024] According to the present invention, there can be provided: a molded article containing a PAS resin and glass fiber and capable of suppressing a decrease in mechanical strength even in a hot water atmosphere and under acidic conditions, a PAS resin composition capable of providing the molded article, and a method for manufacturing them. Detailed Description

[0025] The PAS resin composition of the present invention is characterized in that it is a polyarylene sulfide resin composition prepared by compounding a polyarylene sulfide resin (A), glass fiber (B), and a silane coupling agent (C) as essential components.

[0026] Among them, the glass fiber (B) is a glass fiber containing MgO, CaO, and R2O in a proportion of 6% by mass or more of MgO content, 16% by mass or less of CaO content, and 1% by mass or less of R2O content in the glass fiber (wherein the R2O content represents the total content of Li2O, Na2O, and K2O).

[0027] With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber (B) is in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass. Hereinafter, an explanation will be given.

[0028] The PAS resin composition of the present invention is prepared by compounding a PAS resin (A) as an essential component. The PAS resin (A) has a resin structure having a structure in which an aromatic ring is bonded to a sulfur atom as a repeating unit. Specifically, it is a resin having a structural moiety represented by the following general formula (1) and, if necessary, further having a trifunctional structural moiety represented by the following general formula (2) as a repeating unit.

[0029]

[0030] (In formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.)

[0031]

[0032] With respect to the total number of moles of other structural moieties, the trifunctional structural moiety represented by formula (2) is preferably in the range of 0.001 to 3 mol%, and particularly preferably in the range of 0.01 to 1 mol%.

[0033] Here, in the structural moiety represented by the above general formula (1), particularly from the viewpoint of the mechanical strength of the above PAS resin, R in this formula 1and R 2 Preferably a hydrogen atom. In this case, examples include those bonded in the para position represented by the following formula (3) and those bonded in the meta position represented by the following formula (4).

[0034]

[0035] Among them, especially in terms of the heat resistance and crystallinity of the above PAS resin, the bonding of the sulfur atom in the repeating unit to the aromatic ring is preferably a structure bonded in the para position represented by the above general formula (3).

[0036] In addition, the above PAS resin (A) may not only contain the structural parts represented by the above general formulas (1) and (2), but may also contain the structural parts represented by the following structural formulas (5) to (8) in an amount of 30 mol% or less based on the total of the structural parts represented by the above general formula (1) and general formula (2).

[0037]

[0038] Especially in the present invention, from the viewpoints of the heat resistance and mechanical strength of the PAS resin (A), the structural parts represented by the above general formulas (5) to (8) are preferably 10 mol% or less. When the above PAS resin (A) contains the structural parts represented by the above general formulas (5) to (8), their bonding mode can be either a random copolymer or a block copolymer.

[0039] In addition, the above PAS resin (A) may have a naphthalene thioether bond or the like in its molecular structure, but is preferably 3 mol% or less, particularly preferably 1 mol% or less, relative to the total molar number of other structural parts.

[0040] In addition, as long as the effects of the present invention are not impaired, the physical properties of the PAS resin (A) are not particularly limited, but are as follows.

[0041] (Melt viscosity)

[0042] The melt viscosity of the PAS resin (A) used in the present invention is not particularly limited. From the aspect that the balance between fluidity and mechanical strength becomes good, 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. Among them, in the measurement of the melt viscosity (V6), a rheometer CFT-500D manufactured by Shimadzu Corporation is used, and the PAS resin (A) is held at 300 °C, load: 1.96×10 6 Pa, L / D = 10 (mm) / 1 (mm) for 6 minutes, and then the measured value of the melt viscosity is taken.

[0043] (Non-Newtonian index)

[0044] In the present invention, the non-Newtonian index of the PAS resin (A) used is not particularly limited, and preferably ranges from 0.90 or more to 2.00 or less. When using a linear PAS resin, the non-Newtonian index is preferably in the range of 0.90 or more, more preferably in the range of 0.95 or more, more preferably in the range of 1.50 or less, and more preferably in the range of 1.20 or less. In this way, the mechanical properties, fluidity, and abrasion resistance of the PAS resin (A) are excellent. However, in the present invention, the non-Newtonian index (N value) is a value calculated using the following formula with the shear rate (SR) and shear stress (SS) under the conditions of melting point + 20°C and the ratio of hole length (L) to hole diameter (D) L / D = 40 using a capillary rheometer. The closer the non-Newtonian index (N value) is to 1, the more linear the structure is, and the higher the non-Newtonian index (N value), the greater the structural divergence.

[0045] SR = K·SS N

[0046] [where SR represents the shear rate (seconds -1 ), SS represents the shear stress (dyn / cm 2 ), and K represents a constant.]

[0047] (Manufacturing method)

[0048] As the method for producing the above-mentioned PAS resin (A), there is no particular limitation. For example, there can be mentioned (Production Method 1) a method in which a dihaloaromatic compound is added in the presence of sulfur and sodium carbonate, and a polyhaloaromatic compound or other copolymerization components are added as needed and polymerized; (Production Method 2) a method in which a dihaloaromatic compound is added in a polar solvent in the presence of a thioetherifying agent, etc., and a polyhaloaromatic compound or other copolymerization components are added as needed and polymerized; (Production Method 3) a method in which p-chlorothiophenol is self-condensed by adding other copolymerization components as needed; (Production Method 4) a method in which a diiodoaromatic compound and elemental sulfur are melt-polymerized under reduced pressure in the presence of a polymerization inhibitor optionally having a functional group such as a carboxyl group or an amino group, etc. Among these methods, the method of (Production Method 2) is general and thus preferred. During the reaction, in order to adjust the degree of polymerization, an alkali metal salt of a carboxylic acid, a sulfonic acid, or an alkali metal hydroxide can be added. In the above-mentioned (Production Method 2) method, it is particularly preferably obtained by the following method: an aqueous thioetherifying agent is introduced into a heated mixture containing an organic polar solvent and a dihaloaromatic compound at a rate that can remove water from the reaction mixture, a dihaloaromatic compound, a thioetherifying agent, and a polyhaloaromatic compound used as needed are added in the organic polar solvent and made to react, and the water content in the reaction system is controlled within the range of 0.02 mol or more and 0.5 mol or less relative to 1 mol of the organic polar solvent, whereby a polyarylene sulfide resin is produced (refer to Japanese Patent Laid-Open No. 07-228699); a method in which a dihaloaromatic compound and a polyhaloaromatic compound or other copolymerization components added as necessary are added in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and the reaction is carried out while controlling the alkali metal hydrosulfide and the organic alkali metal salt within the range of 0.01 mol or more and 0.9 mol or less of the organic alkali metal salt relative to 1 mol of the sulfur source, and controlling the water content in the reaction system within the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent (refer to WO2010 / 058713 pamphlet).As specific examples of the dihaloaromatic compound, 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'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and compounds having an alkyl group with 1 to 18 carbon atoms on the aromatic ring of each of the above compounds can be cited. As the polyhaloaromatic compound, 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. can be cited. In addition, the halogen atoms contained in each of the above compounds are preferably chlorine atoms and bromine atoms.

[0049] As a method for post-treating the reaction mixture containing the PAS resin (A) obtained through the polymerization step, there is no particular limitation, and examples thereof include: (Post-treatment 1) After the polymerization reaction is completed, first, the reaction mixture is directly, or after adding an acid or a base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid matter after the solvent is distilled off is washed with water, a reaction solvent (or an organic solvent having the same solubility as the low molecular polymer), acetone, methyl ethyl ketone, alcohols, etc. one or more times, and further 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 that is soluble in the polymerization solvent used and is at least a poor solvent for the PAS resin) is added to the reaction mixture as a precipitant to precipitate solid products such as the PAS resin and inorganic salts, and these precipitates are filtered, washed, and dried; or (Post-treatment 3) After the polymerization reaction is completed, a reaction solvent (or an organic solvent having the same solubility as the low molecular polymer) is added to the reaction mixture and stirred, and then the low molecular weight polymer is filtered off, and the resulting product is washed with water, acetone, methyl ethyl ketone, alcohols, etc. one or more times, and then neutralized, washed with water, filtered, and dried; (Post-treatment 4) After the polymerization reaction is completed, water is added to the reaction mixture for washing with water and filtering, and if necessary, an acid is added during the washing with water for acid treatment, and then dried; (5) After the polymerization reaction is completed, the reaction mixture is filtered, and if necessary, washed with the reaction solvent one or more times, and further washed with water, filtered, and dried, etc.

[0050] It should be noted that in the post-treatment methods exemplified in the above (post-treatment 1) to (post-treatment 5), the drying of the PAS resin (A) can be carried out in a vacuum, or in air or an inert gas atmosphere such as nitrogen.

[0051] The PAS resin composition of the present invention is compounded with glass fiber (B) as an essential component. The glass fiber (B) contains MgO in an amount greater than 5% by mass, contains CaO in an amount of 16% by mass or less, and contains R2O in an amount of 1% by mass or less.

[0052] The content of MgO in the glass fiber is greater than 5% by mass, preferably 6% by mass or more, and the upper limit is not specified, preferably in the range of 15% by mass or less, more preferably 10% by mass or less. In addition, the content of CaO in the glass fiber is 16% by mass or less, preferably less than 16% by mass. In addition, the lower limit is not specified, but preferably 13% by mass or more. Furthermore, the content of R2O in the glass fiber (wherein R2O is the general term for Li2O, Na2O, and K2O. The R2O content represents the total content of Li2O, Na2O, and K2O) is 1% by mass or less, preferably less than 1% by mass, and the lower limit is not specified, but preferably 0% by mass. By making the ratio of MgO to CaO content in the glass fiber high and further making the R2O content rate in this range, the dissolution of the glass component in an acid, alkali, and humid heat environment can be suppressed, and at the same time, the chemical resistance and mechanical strength can be balanced.

[0053] B2O3 can be optionally contained in the glass fiber. The content of B2O3 in the glass fiber is arbitrary, so there is no particular limitation. It is preferably less than 1% by mass, more preferably 0% by mass, thereby suppressing the dissolution of the glass component in an acid, alkali, and humid heat environment and improving the balance between chemical resistance and mechanical strength.

[0054] Aluminum oxide (Al2O3) can be optionally contained in the glass fiber. The content of aluminum oxide in the glass fiber is arbitrary, so there is no particular limitation, but it is preferably 10% by mass or more, more preferably 13% by mass or more, preferably 20% by mass or less, more preferably 16% by mass or less.

[0055] The balance contains silicon oxide (SiO 2) . The silicon oxide content can be the balance of the above components and is not particularly limited. In the glass fiber, it is preferably 65% by mass or less and preferably 60% by mass or more.

[0056] By compounding these glass fibers (B), a molded product with excellent heat and humidity resistance, acid resistance, alkali resistance, and mechanical strength can be obtained.

[0057] With respect to 100 parts by mass of the PAS resin (A), the compounding amount of the above glass fiber (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably in the range of 30 parts by mass or more, and preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably in the range of 60 parts by mass or less. By making the compounding amount of the above glass fiber (B) within this range, a molded article excellent in heat and humidity resistance, acid resistance, alkali resistance, and mechanical strength can be obtained.

[0058] The PAS resin composition of the present invention compounded with a silane coupling agent (C) as an essential component. As the silane coupling agent (C) used in the present invention, there is no particular limitation as long as the effects of the present invention are not impaired, and examples thereof include silane coupling agents preferably having a functional group reactive with a carboxyl group such as an epoxy group, an isocyanate group, an amino group, or a hydroxyl group. As such silane coupling agents, for example, epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanate group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane; hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane. In the present invention, the silane coupling agent (C) is not an essential component, but at the time of compounding, as long as the effects of the present invention are not impaired, there is no particular limitation on its addition amount, and with respect to 100 parts by mass of the PAS resin (A), its compounding amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably in the range of 5 parts by mass or less. Within this range, a molded article excellent in heat and humidity resistance, acid resistance, alkali resistance, and mechanical strength can be obtained.

[0059] The PAS resin composition of the present invention may compound a thermoplastic elastomer (D) as an optional component. As such thermoplastic elastomer, polyolefin-based elastomers, fluorine-based elastomers, or silicone-based elastomers can be cited, among which polyolefin-based elastomers are preferred. With respect to 100 parts by mass of the PAS resin (A), the compounding amount of these thermoplastic elastomers (D) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 20 parts by mass or less, more preferably in the range of 15 parts by mass or less. Within this range, a molded article excellent in heat and humidity resistance, acid resistance, alkali resistance, mechanical strength, particularly impact resistance can be obtained.

[0060] For example, the above-mentioned polyolefin-based elastomers include homopolymers of α-olefins, copolymers of two or more α-olefins, and copolymers of one or two or more α-olefins and vinyl polymerizable compounds having functional groups. At this time, as the above-mentioned α-olefins, α-olefins in the range of 2 or more to 8 or less carbon atoms such as ethylene, propylene, 1-butene, etc. can be mentioned. In addition, as the above-mentioned functional groups, carboxyl group, acid anhydride group (-C(=O)OC(=O)-), epoxy group, amino group, hydroxyl group, mercapto group, isocyanate group, oxazoline group, etc. can be mentioned. Moreover, as the above-mentioned vinyl polymerizable compounds having functional groups, 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, butyl acrylate, etc.; metal salts of α,β-unsaturated carboxylic acids such as ionomers (as the metal, alkali metals such as sodium, alkaline earth metals such as calcium, zinc, etc. can be mentioned); glycidyl esters of α,β-unsaturated carboxylic acids such as glycidyl methacrylate, etc.; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc.; derivatives (monoester, diester, acid anhydride) of the above-mentioned α,β-unsaturated dicarboxylic acids, etc., one or more of these can be mentioned. The above-mentioned thermoplastic elastomers can be used alone or in combination of two or more.

[0061] In the present invention, a fibrous filler other than the glass fiber (B) which is the above-mentioned essential component (hereinafter also referred to as "other fibrous filler") can also be compounded as an optional component. As such other fibrous fillers, for example, glass fibers other than the above-mentioned glass fiber (B), carbon fibers, silane glass fibers, ceramic fibers, aromatic polyamide fibers, metal fibers, etc. can be mentioned, and one or two or more of them can be compounded.

[0062] Although it is an optional component, when compounding, relative to 100 parts by mass of the PAS resin (A), the compounding amount of the fibrous filler is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably in the range of 15 parts by mass or more, and preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 150 parts by mass or less. By making the compounding amount of the fibrous filler within these ranges, better effects can be obtained in maintaining the mechanical strength of the molded product.

[0063] As the fibrous filler material, a material processed with a surface treatment agent or a bundling agent can also be used. Thereby, the adhesion to the PAS resin (A) can be improved, so it is preferred. As the above-mentioned surface treatment agent or bundling agent, for example, at least one polymer selected from the group consisting of silane compounds, titanate compounds, acrylic resins, polyurethane resins, and epoxy resins having functional groups such as amino group, epoxy group, isocyanate group, vinyl group, etc. can be mentioned.

[0064] The PAS resin composition of the present invention may, if necessary, further incorporate other fillers (hereinafter also referred to as "other fillers") other than the above-mentioned glass fiber (B) as an essential component and other fibrous fillers as optional components as optional components. As these other fillers, as long as the effects of the present invention are not impaired, publicly known and commonly used materials can be used, such as fillers in various shapes such as granular or plate-like. In addition, non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, palygorskite, ferrite, calcium silicate, calcium carbonate, glass beads, zeolite, ground fibers, calcium sulfate, etc. can also be used.

[0065] In the present invention, other fillers are not essential components, but when compounding, as long as the effects of the present invention are not impaired, their compounding amounts are not particularly limited. As the compounding amount of other fillers, for example, relative to 100 parts by mass of the PAS resin (A), it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, preferably 600 parts by mass or less, and more preferably 200 parts by mass or less. Within this range, the resin composition exhibits good mechanical strength and moldability, so it is preferred.

[0066] Furthermore, in addition to the above components, the PAS resin composition of the present invention may appropriately incorporate 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, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polystyrene resin, ABS resin, phenolic resin, polyurethane resin, liquid crystal polymer, etc. (hereinafter simply referred to as synthetic resins) as optional components. In the present invention, the above synthetic resins are not essential components, but when compounding, as long as the effects of the present invention are not impaired, their compounding ratios are not particularly limited. In addition, they vary depending on each purpose and cannot be generalized. As the ratio of the synthetic resin compounded in the resin composition of the present invention, for example, it can be cited as a range of 5 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the PAS resin (A). In other words, relative to the total of the PAS resin (A) and the synthetic resin, the ratio of the PAS resin (A) is preferably in the range of (100 / 115) or more and more preferably in the range of (100 / 105) or more on a mass basis.

[0067] In addition, the PAS resin composition of the present invention 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, esters of fatty acids having 18 to 30 carbon atoms such as stearic acid and montanic acid, polyolefin waxes such as polyethylene, etc.), which are compounded as optional components. These additives are not essential components. For example, with respect to 100 parts by mass of the PAS resin (A), it is preferably in the range of 0.01 part by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 10 parts by mass or less. They can be appropriately adjusted and used according to the purpose without impairing the effects of the present invention.

[0068] The manufacturing method of the polyarylene sulfide resin composition of the present invention is characterized by having a step of compounding a polyarylene sulfide resin (A), glass fiber (B), and a silane coupling agent (C) as essential components and performing melt-kneading in a temperature range above the melting point of the polyarylene sulfide resin (A).

[0069] The glass fiber (B) is a glass fiber containing MgO, CaO, and R2O in a proportion of 6% by mass or more of MgO content, 16% by mass or less of CaO content, and 1% by mass or less of R2O content in the glass fiber (wherein the R2O content represents the total content of Li2O, Na2O, and K2O).

[0070] With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber (B) is in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass.

[0071] The following is a detailed description.

[0072] The manufacturing method of the PAS resin composition of the present invention has a step of compounding the above essential components and performing melt-kneading in a temperature range above the melting point of the PAS resin (A). More specifically, the PAS resin composition of the present invention is composed of each essential component and other optional components as required. As a method for manufacturing the resin composition used in the present invention, there is no particular limitation, and examples thereof include a method of compounding essential components and optional components as required and performing melt-kneading. More specifically, examples include a method of uniformly performing dry mixing using a drum or a Henschel mixer as required, and then charging into a twin-screw extruder for melt-kneading.

[0073] The melt-kneading can be carried out by heating to a temperature range above the melting point of the PAS resin (A), preferably to a temperature range of the melting point +10°C or higher, more preferably the melting point +10°C or higher, further preferably the melting point +20°C or higher, preferably to a temperature range of the melting point +100°C or lower, and more preferably the melting point +50°C or lower.

[0074] As the above-mentioned melt-kneading machine, from the viewpoints of dispersibility and productivity, a twin-screw kneading extruder is preferred. For example, it is preferred to carry out melt-kneading while appropriately adjusting the discharge amount of the resin component in the range of 5 to 500 (kg / hr) and the screw rotation speed in the range of 50 to 500 (rpm). Further preferably, melt-kneading is carried out under the condition that their ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). In addition, the addition and mixing of each component into the melt-kneading machine can be carried out simultaneously or batchwise. For example, when adding the essential component of glass fiber (B) and other fibrous fillers as required to the above components, from the viewpoint of dispersibility, it is preferred to feed them into the extruder from the side feeder of the above twin-screw kneading extruder. Regarding the position of this side feeder, the ratio of the distance from the resin feeding part (top feeder) of the above twin-screw kneading extruder to this side feeder to the total length of the screw of the above twin-screw kneading extruder is preferably 0.1 or more, and more preferably 0.3 or more. In addition, this ratio is preferably 0.9 or less, and more preferably 0.7 or less.

[0075] The PAS resin composition of the present invention obtained by such melt-kneading is a molten mixture containing the above-mentioned essential components, as well as optional components added as required and components derived from them. Therefore, the PAS resin (A) of the PAS resin composition of the present invention forms a continuous phase and has a morphology in which other essential components and optional components are dispersed. After the melt-kneading of the PAS resin composition of the present invention, it is preferably pre-dried in a temperature range of 100 to 150°C by a known method, for example, after extruding and molding the molten resin composition into a linear shape and then processing it into forms such as pellets, sheets, granules, powders, etc. as required.

[0076] The molded article of the present invention is obtained by melt-molding the PAS resin composition. In addition, the manufacturing method of the molded article of the present invention has a step of melt-molding the above-mentioned PAS resin composition. Therefore, the PAS resin (A) of the molded article of the present invention forms a continuous phase and has a morphology in which other essential components and optional components other than the PAS resin (A) are dispersed. By having such a morphology, the PAS resin composition can obtain a molded article with excellent heat and humidity resistance, acid resistance, alkali resistance, and mechanical strength.

[0077] The PAS resin composition of the present invention can be used for various molding methods such as injection molding, compression molding, composite materials, extrusion molding of sheets, tubes, etc., drawing molding, blow molding, transfer molding, etc. However, its mold release property is particularly excellent, so it is suitable for injection molding applications. When molding by injection molding, various molding conditions are not particularly limited, and generally, molding can be carried out by a general method. For example, in an injection molding machine, after melting the above-mentioned PAS resin composition at a resin temperature in a temperature range above the melting point of the PAS resin (A), preferably in a temperature range of the melting point + 10°C or more, more preferably in a temperature range of the melting point + 10°C to the melting point + 100°C, and further preferably in a temperature range of the melting point + 20°C to the melting point + 50°C, it can be molded by injecting it into a mold through a resin extrusion port. At this time, the mold temperature is also set within a known temperature range, for example, room temperature (23°C) to 300°C, and preferably set to 120 to 180°C.

[0078] Examples of products that are molded articles of the PAS resin composition of the present invention include, for example, pipes, liner pipes, cap nuts, pipe fittings, (elbows, headers, T-pipes, reducers, joints, couplers, etc.), various valves, flow meters, gaskets (sealing, closing types), etc., and various components attached to pipes for fluid transportation (also referred to as "fluid transportation components" in the present invention). Therefore, examples include various pipes related to fuel, exhaust systems, and intake systems, air intake nozzles, intake manifolds, fuel pumps, engine coolant joints, outlet parts, etc., that are attached to internal combustion engines such as automotive parts, and they can also be applied to various other uses. Furthermore, heat dissipation components for engine control units or motors in automobiles, heat dissipation components for LED substrates, and radiators for various electrical / electronic equipment substrates can also be exemplified. In addition, the molded article of the present invention can be not only made into a heat dissipation component but also made into the following ordinary resin molded articles.Examples of electrical / electronic components include protective / support components for box-type electrical / electronic component integrated modules, multiple individual semiconductors or modules, sensors, LED lights, connectors, sockets, resistors, relay boxes, switches, bobbin holders, capacitors, rheostat boxes, optical pickups, oscillators, transformers, plugs, printed circuit boards, tuners, microphones, headphones, small motors, head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD sliders, FDD carriers, motor brush holders, parabolic antennas, computer-related components, etc.; household and office electrical product components represented by VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, sound / video equipment components such as audio / laser disc / CD / DVD / Blu-ray disc, lighting components, refrigerator components, air conditioner components, typewriter components, word processor components, or water usage site equipment components such as water heaters, hot water volume and temperature sensors in bathtubs, etc.; mechanical-related components represented by office computer-related components, telephone-related components, fax-related components, copier-related components, cleaning jigs, motor components, lighters, typewriters, etc.; optical equipment and precision mechanical-related components represented by microscopes, binoculars, cameras, watches, etc.; various valves such as alternator terminals, alternator connectors, brush holders, slip rings, IC regulators, potentiometer bases for dimmers, relay blocks, circuit breakers, exhaust valves, etc., various pipes for fuel-related / exhaust system / intake system, intake nozzle vent pipes, intake manifolds, fuel pumps, engine coolant connectors, carburetor bodies, carburetor gaskets, exhaust sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle valve position sensors, crankshaft position 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 pump impellers, turbine blades, wiper motor-related components, distributors, starter switches, ignition coils and their bobbin holders, motor insulators, motor rotors, motor cores, starter relays, wiring harnesses for transmissions, window washer nozzles, air conditioner panel switch substrates, coils for fuel-related solenoid valves, connectors for fuses, horn terminals, insulation boards for electronic control components, stepper motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbin holders, oil filters, ignition device housings, power modules, inverters, power devices, intelligent power modules, insulated gate bipolar transistors, power control units, reactors, torque converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, junction boxes, ignition coils for DLI systems, etc., storage housings for automotive / vehicle-related components, and other various uses.

[0079] Embodiment

[0080] Hereinafter, examples and comparative examples will be used for illustration, but the present invention is not limited to these examples. It should be noted that hereinafter, unless otherwise specified, "%" or "parts" are based on mass.

[0081] <Examples 1 to 5 and Comparative Examples 1 to 2>

[0082] Mix each material according to the composition and compounding amount shown in Table 1. Then, put these compounded materials into a twin-screw extruder "TEX-30α (product name)" with exhaust holes manufactured by Japan Steel Works, Ltd., with a resin component discharge rate of 30 kg / hr and a screw rotation speed of 200 rpm. Melt and knead at a set resin temperature of 320 °C to obtain pellets of the resin composition. Glass fiber is fed from the side feeder, and the other materials are pre-mixed evenly by a tumbler and fed from the top feeder. After drying the obtained pellets of the resin composition in a gear oven at 140 °C for 2 hours, various test pieces are produced by injection molding and the following tests are carried out.

[0083] <Tensile strength>

[0084] Supply the obtained pellets to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a barrel temperature set at 310 °C, and use a mold for molding ISO Type-A dumbbell sheets with a mold temperature adjusted to 140 °C to perform injection molding to obtain ISO Type-A dumbbell sheets. It should be noted that in order to obtain a test piece without a welded part, the resin is injected from a single-point gate of an ISO D2 sheet. The tensile strength of the obtained dumbbell sheets is measured according to the measurement method based on ISO 527-1 and 2.

[0085] <Flexural strength, flexural modulus>

[0086] Measure the flexural strength and flexural modulus of the above ISO TYPE-A dumbbell sheets according to the measurement method based on ISO 178.

[0087] <Impact strength>

[0088] Cut the central part of the dumbbell-shaped test piece for tensile test into a rod shape with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, and after notch processing, make it into an impact resistance test piece, and perform a Charpy impact test according to ISO179-1 / 1eA to measure the impact strength (kJ / mm 2 ).

[0089] <Linear thermal expansion coefficient>

[0090] Cut the central part of the dumbbell-shaped test piece for the tensile test into a rectangular parallelepiped with a length of 10 mm, a width of 10 mm, and a thickness of 4 mm, and use it as the linear thermal expansion coefficient test piece. Measure it according to ISO 11359-2, and measure the linear thermal expansion coefficient parallel to the flow direction in the temperature range of -50 to 50 °C.

[0091] <Acid resistance test>

[0092] For Method A, after immersing in 46% hydrofluoric acid (reagent special grade manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) at room temperature for 100 hours, measure the tensile strength. Further, divide by the tensile strength of the material before immersion to calculate the retention rate. The results are shown in Tables 1 and 2.

[0093] For Method B, after immersing in Sanpoll stock solution (9.5% hydrochloric acid manufactured by Dainippon Jochugiku Co., Ltd., containing a surfactant (alkyltrimethylammonium)) at room temperature for 500 hours, measure the tensile strength. Further, divide by the tensile strength of the material before immersion to calculate the retention rate. The results are shown in Tables 1 and 2.

[0094] <Alkali resistance test>

[0095] For Method C, after immersing in Domestos Disinfectant Cleaner stock solution (manufactured by Unilever Japan K.K., an alkaline cleaning agent containing about 3.8% sodium hypochlorite, about 1.4% sodium hydroxide, and a surfactant (main component alkylamine oxide)) at room temperature for 500 hours, measure the tensile strength. Further, divide by the tensile strength of the material before immersion to calculate the retention rate. The results are shown in Tables 1 and 2.

[0096] [Table 1]

[0097] Example 1 Example 2 Example 3 Example 4 A 1 100 100 - - A2 - - 100 - A3 - - - 100 A4 - - - - B 1 67.0 46.4 67.0 67.0 B 2 - - - - C1 0.5 0.5 0.5 0.5 D1 - 7.7 - - Tensile Strength MPa 200 155 201 198 Flexural Strength MPa 296 243 298 291 Flexural Modulus of Elasticity GPa 17.4 11.0 17.4 17.8 Impact Strength <![CDATA[kJ / m 2 > 10.2 13.9 10.4 10.0 Linear Thermal Expansion Coefficient <![CDATA[×10 -6 / K]]> 12.1 14.0 12.4 11.9 Tensile Strength by Method A MPa 183 147 180 177 Retention Rate ％ 92％ 95％ 90％ 89％ Tensile Strength by Method B MPa 194 153 194 193 Retention Rate ％ 97％ 99％ 97％ 97％ Tensile Strength by Method C MPa 191 152 195 192 Retention Rate ％ 96％ 98％ 97％ 97％

[0098] [Table 2]

[0099] Example 5 Comparative Example 1 Comparative Example 2 A 1 - 100 100 A 2 - - - A3 - - - A4 100 - - B 1 67.0 - - B 2 - 67.0 46.4 C1 0.5 0.5 0.5 D1 - - 7.7 Tensile Strength MPa 192 192 151 Flexural Strength MPa 278 276 230 Flexural Modulus of Elasticity GPa 16.8 15.5 9.5 Impact Strength <![CDATA[kJ / m 2 > 9.8 9.5 13.5 Linear Thermal Expansion Coefficient <![CDATA[×10 -6 / K]]> 12.7 13.2 15.1 Tensile Strength by Method A MPa 165 152 127 Retention Rate ％ 86％ 79％ 84％ Tensile Strength by Method B MPa 185 180 144 Retention Rate ％ 96％ 94％ 95％ Tensile Strength by Method C MPa 180 176 140 Retention Rate ％ 94％ 92％ 93％

[0100] It should be noted that the compounding ratios of the compounding components in Tables 1 and 2 are expressed in parts by mass, and the following substances are used.

[0101] ·PAS resin component

[0102] Polyphenylene sulfide resin

[0103] A1: Melt viscosity 56 Pa·s, non-Newtonian index 1.07

[0104] A2: Melt viscosity 180 Pa·s, non-Newtonian index 1.07

[0105] A3: Melt viscosity 7 Pa·s, non-Newtonian index 1.07

[0106] A4: melt viscosity 700 Pa·s, non-Newtonian index 1.60

[0107] (Production Example 1) Production of polyphenylene sulfide resin (A1)

[0108] [Step 1]

[0109] In a 150-liter autoclave equipped with a stirrer blade, a pressure gauge, a thermometer, a condenser, a decanter, and a rectifying column, 33.075 parts by mass (225 parts by mole) of p-dichlorobenzene (hereinafter abbreviated as "p-DCB"), 3.420 parts by mass (34.5 parts by mole) of NMP, 27.300 parts by mass of a 47.23 mass% aqueous NaSH solution (230 parts by mole as NaSH), and 18.533 parts by mass of a 49.21 mass% aqueous NaOH solution (228 parts by mole as NaOH) were added. While stirring, the temperature was raised to 173°C in a nitrogen atmosphere over 5 hours. After distilling off 27.300 parts by mass of water, the autoclave was sealed. The p-DCB distilled off by azeotropic distillation during dehydration was separated in the decanter and returned to the autoclave at any time. Inside the autoclave after dehydration, an anhydrous sodium sulfide composition in the form of fine particles was dispersed in p-DCB. The NMP content in this composition was 0.079 parts by mass (0.8 parts by mole), so it means that 98 mol% (33.7 parts by mole) of the NMP charged was hydrolyzed into the sodium salt of the NMP ring-opened product (4-(methylamino)butyric acid) (hereinafter abbreviated as "SMAB"). The amount of SMAB in the autoclave was 0.147 parts by mole relative to 1 mole of sulfur atoms present in the autoclave. The theoretical water dehydration amount when all the NaSH and NaOH charged became anhydrous Na2S was 27.921 parts by mass. Therefore, it means that out of the 0.878 parts by mass (48.8 parts by mole) of residual water in the autoclave, 0.609 parts by mass (33.8 parts by mole) was consumed by the hydrolysis reaction of NMP and NaOH and did not exist in the autoclave in the form of water, and the remaining 0.269 parts by mass (14.9 parts by mole) remained in the autoclave in the form of water or crystal water. The amount of water in the autoclave was 0.065 moles relative to 1 mole of sulfur atoms present in the autoclave.

[0110] [Step 2]

[0111] After the above dehydration process is completed, cool the internal temperature to 160 °C, charge 46.343 parts by mass (467.5 parts by mole) of NMP, and heat up to 185 °C. The amount of water in the autoclave is 0.025 mole per 1 mole of NMP charged in Step 2. When the gauge pressure reaches 0.00 MPa, open the valve connecting to the distillation column and heat up to an internal temperature of 200 °C over 1 hour. At this time, control the cooling and valve opening to keep the outlet temperature of the distillation column below 110 °C. Condense the mixed vapor of distilled p-DCB and water with a condenser and separate it with a decanter. Return the p-DCB to the autoclave. The amount of distilled water is 0.228 parts by mass (12.7 parts by mole).

[0112] [Step 3]

[0113] At the start of Step 3, the amount of water in the autoclave is 0.041 parts by mass (2.3 parts by mole), which is 0.005 mole per 1 mole of NMP added in Step 2 and 0.010 mole per 1 mole of sulfur atoms present in the autoclave. The amount of SMAB in the autoclave is the same as in Step 1, which is 0.147 mole per 1 mole of sulfur atoms present in the autoclave. Then, heat up from an internal temperature of 200 °C to 230 °C over 3 hours, stir for 1 hour at 230 °C, then heat up to 250 °C and stir for 1 hour. The gauge pressure is 0.03 MPa at an internal temperature of 200 °C, and the final gauge pressure is 0.40 MPa. After cooling, in the resulting slurry, inject 0.650 parts by mass into 3 parts by mass (3 liters) of water, stir at 80 °C for 1 hour, and then filter. Stir the filter cake with 3 parts by mass (3 liters) of warm water for 1 hour, wash, and then filter. Repeat this operation 4 times. Add 3 parts by mass (3 liters) of warm water and acetic acid to the filter cake, adjust the pH to 4.0, stir for 1 hour, wash, and then filter. Stir the filter cake with 3 parts by mass (3 liters) of warm water for 1 hour, wash, and then filter. Repeat this operation 2 times. Dry overnight at 120 °C using a hot air dryer to obtain a white powdery PPS resin (A1). The melt viscosity of this polymer at 300 °C is 56 Pa·s. The non-Newtonian index is 1.07.

[0114] (Production Example 2) Production of polyphenylene sulfide resin (A2)

[0115] [Step 1]

[0116] In a 150 L autoclave equipped with a stirrer blade and connected to a manometer, a thermometer, a capacitor, a decanter, and a distillation column, 33.222 parts by mass (226 parts by mole) of p-DCB, 3.420 parts by mass (34.5 parts by mole) of NMP, 27.300 parts by mass of a 47.23 mass% aqueous solution of NaSH (230 parts by mole as NaSH), and 18.533 parts by mass of a 49.21 mass% aqueous solution of NaOH (228 parts by mole as NaOH) were charged. While stirring, the temperature was raised to 173 °C in a nitrogen atmosphere over 5 hours. After distilling off 27.300 parts by mass of water, the autoclave was sealed. The p-DCB distilled off by azeotropic distillation during dehydration was separated in the decanter and returned to the autoclave at any time. Inside the autoclave after dehydration, a particulate anhydrous sodium sulfide composition was dispersed in p-DCB. The NMP content in this composition was 0.079 parts by mass (0.8 parts by mole), so it means that 98 mol% (33.7 parts by mole) of the charged NMP was hydrolyzed into the ring-opened form SMAB of NMP. The amount of SMAB in the autoclave was 0.147 parts by mole relative to 1 mole of sulfur atoms present in the autoclave. The theoretical water removal amount when all the charged NaSH and NaOH were converted into anhydrous Na2S was 27.921 parts by mass. Therefore, it means that among the residual water amount of 0.878 parts by mass (48.8 parts by mole) in the autoclave, 0.609 parts by mass (33.8 parts by mole) was consumed by the hydrolysis reaction of NMP and NaOH and did not exist in the autoclave in the form of water, and the remaining 0.269 parts by mass (14.9 parts by mole) remained in the autoclave in the form of water or water of crystallization. The water amount in the autoclave was 0.065 moles relative to 1 mole of sulfur atoms present in the autoclave.

[0117] [Process 2]

[0118] After the above dehydration process was completed, the internal temperature was cooled to 160 °C, 46.343 parts by mass (467.5 parts by mole) of NMP was charged, and the temperature was raised to 185 °C. The water amount in the autoclave was 0.025 moles relative to 1 mole of NMP added in Process 2. When the gauge pressure reached 0.00 MPa, the valve connected to the distillation column was opened, and the temperature was raised to an internal temperature of 200 °C over 1 hour. At this time, the cooling and valve opening were controlled so that the distillation column outlet temperature was below 110 °C. The mixed vapor of distilled p-DCB and water was condensed by a condenser and separated by a decanter, and the p-DCB was returned to the autoclave. The amount of distilled water was 0.228 parts by mass (12.7 parts by mole).

[0119] [Process 3]

[0120] At the start of Step 3, the amount of water in the autoclave was 0.041 parts by mass (2.3 moles), which was 0.005 moles relative to 1 mole of NMP added in Step 2 and 0.010 moles relative to 1 mole of sulfur atoms present in the autoclave. The amount of SMAB in the autoclave was the same as in Step 1, which was 0.147 moles relative to 1 mole of sulfur atoms present in the autoclave. Next, the internal temperature was raised from 200 °C to 230 °C over 3 hours, stirred at 230 °C for 3 hours, then raised to 250 °C and stirred for 1 hour. The gauge pressure was 0.03 MPa at an internal temperature of 200 °C and the final gauge pressure was 0.40 MPa. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the resulting slurry, stirred at 80 °C for 1 hour, and then filtered. The filter cake was further stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed, and then filtered. This operation was repeated 4 times. The filter cake was further added with 3 parts by mass (3 liters) of warm water and acetic acid, the pH was adjusted to 4.0, stirred for 1 hour, washed, and then filtered. The filter cake was further stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed, and then filtered. This operation was repeated twice. It was dried overnight at 120 °C using a hot air dryer to obtain a white powdery PPS resin (A2). The melt viscosity of this polymer at 300 °C was 180 Pa·s. The non-Newtonian index was 1.07.

[0121] (Production Example 3) Production of polyphenylene sulfide resin (A3)

[0122] [Step 1]

[0123] In a 150-L autoclave equipped with a stirrer blade and connected to a manometer, a thermometer, a capacitor, a decanter, and a rectifying column, 35.868 parts by mass (244 parts by mole) of p-DCB, 3.420 parts by mass (34.5 parts by mole) of NMP, 27.300 parts by mass of a 47.23 mass% aqueous solution of NaSH (230 parts by mole as NaSH), and 18.533 parts by mass of a 49.21 mass% aqueous solution of NaOH (228 parts by mole as NaOH) were added. While stirring, the temperature was raised to 173 °C in a nitrogen atmosphere over 5 hours. After distilling off 27.300 parts by mass of water, the autoclave was sealed. The p-DCB distilled off by azeotropic distillation during dehydration was separated in the decanter and returned to the autoclave at any time. Inside the autoclave after dehydration, a particulate anhydrous sodium sulfide composition was dispersed in p-DCB. The NMP content in this composition was 0.079 part by mass (0.8 part by mole), and thus it means that 98 mol% (33.7 parts by mole) of the charged NMP was hydrolyzed to the ring-opened product SMAB of NMP. The amount of SMAB in the autoclave was 0.147 part by mole relative to 1 mole of sulfur atoms present in the autoclave. The theoretical amount of water to be removed when all of the charged NaSH and NaOH were converted to anhydrous Na2S was 27.921 parts by mass. Thus, it means that among the 0.878 part by mass (48.8 parts by mole) of the residual water amount in the autoclave, 0.609 part by mass (33.8 parts by mole) was consumed by the hydrolysis reaction of NMP and NaOH and did not exist in the autoclave in the form of water, and the remaining 0.269 part by mass (14.9 parts by mole) remained in the autoclave in the form of water or water of crystallization. The amount of water in the autoclave was 0.065 mole relative to 1 mole of sulfur atoms present in the autoclave.

[0124] [Process 2]

[0125] After the above dehydration process was completed, the internal temperature was cooled to 160 °C, 46.343 parts by mass (467.5 parts by mole) of NMP was added, and the temperature was raised to 185 °C. The amount of water in the autoclave was 0.025 mole relative to 1 mole of the NMP charged in Process 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 °C over 1 hour. At this time, the cooling and the valve opening were controlled so that the temperature at the outlet of the rectifying column was 110 °C or lower. The mixed vapor of distilled p-DCB and water was condensed by a condenser and separated by a decanter, and the p-DCB was returned to the autoclave. The amount of distilled water was 0.228 part by mass (12.7 parts by mole).

[0126] [Process 3]

[0127] At the start of Process 3, the amount of water in the autoclave was 0.041 parts by mass (2.3 moles), which is 0.005 moles relative to 1 mole of NMP added in Process 2 and 0.010 moles relative to 1 mole of sulfur atoms present in the autoclave. The amount of SMAB in the autoclave was the same as in Process 1, which is 0.147 moles relative to 1 mole of sulfur atoms present in the autoclave. Next, the internal temperature was raised from 200 °C to 230 °C over 3 hours, stirred at 230 °C for 1 hour, then raised to 250 °C and stirred for 1 hour. The gauge pressure was 0.03 MPa at an internal temperature of 200 °C, and the final gauge pressure was 0.40 MPa. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the resulting slurry, stirred at 80 °C for 1 hour, and then filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed, and then filtered. This operation was repeated 4 times. The filter cake was further added to 3 parts by mass (3 liters) of warm water and acetic acid, the pH was adjusted to 4.0, stirred for 1 hour, washed, and then filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed, and then filtered. This operation was repeated twice. It was dried overnight at 120 °C using a hot air dryer to obtain a white powdery PPS resin (A3). The melt viscosity of this polymer at 300 °C was 7 Pa·s. The non-Newtonian index was 1.07.

[0128] (Production Example 4) Production of polyphenylene sulfide resin (A4)

[0129] In a 150-liter autoclave equipped with a pressure gauge, thermometer, stirring blade with a capacitor, and a bottom valve, 19.413 parts by mass of flaky sodium sulfide (60.3 mass% Na2S) and 45.000 parts by mass of NMP were added. While stirring under a nitrogen stream, the temperature was raised to 209 °C, and 4.644 parts by mass of water was distilled off (the remaining water content was 1.13 moles per mole of sodium sulfide). After that, the autoclave was sealed and cooled to 180 °C, and 22.05 parts by mass of p-DCB and 18.000 parts by mass of NMP were added. Pressurized with nitrogen to a gauge pressure of 0.1 MPa at a liquid temperature of 150 °C and started heating. Stirred at a liquid temperature of 260 °C for 3 hours to allow the reaction to proceed, and cooled by sprinkling water on the upper part of the autoclave. Next, while cooling, the cooling of the upper part of the autoclave was stopped. When cooling the upper part of the autoclave, the liquid temperature was kept constant without dropping. The maximum pressure during the reaction was 0.85 MPa.

[0130] After the reaction, it was cooled. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the resulting slurry, stirred at 80 °C for 1 hour, and then filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed, and then filtered. This operation was repeated 7 times. It was dried overnight at 120 °C using a hot air dryer.

[0131] Then, it was heat-treated at 250 °C for 3 hours using a hot air dryer to obtain a PPS resin (A4). The obtained polymer had a melt viscosity of 700 Pa·s and a non-Newtonian index of 1.60.

[0132] · Glass fiber

[0133] B1: Glass fiber manufactured by Nippon Electric Glass Co., Ltd. (MgO content 8 wt%, CaO content 14.5 wt%, R2O content 0.5 wt% or less, Al2O3 content 16 wt%, balance SiO2), average fiber length 3 mm, average fiber diameter 10 μm

[0134] B2: E glass “T-717H” manufactured by Nippon Electric Glass Co., Ltd. (MgO content 2.5 wt%, CaO content 20.5 wt%, R2O content 1.5 wt% or less, Al2O3 content 14 wt%, balance SiO2), average fiber length 3 mm, average fiber diameter 10 μm.

[0135] · Silane coupling agent

[0136] C1: “SH-6040” 3-glycidoxypropyltrimethoxysilane manufactured by Dow Corning Corporation

[0137] · Thermoplastic elastomer

[0138] D1: “BONDFAST 7m” manufactured by Sumitomo Chemical Co., Ltd., as a copolymer component, containing 67 mass% ethylene, 6 mass% glycidyl methacrylate, and 27 mass% methyl acrylate.

Claims

1. A polyarylene sulfide resin composition, characterized in that, It is a polyphenylene sulfide resin composition prepared by compounding polyphenylene sulfide resin (A), glass fiber (B), and silane coupling agent (C) as essential components. The glass fiber (B) is a glass fiber containing MgO, CaO, and R2O in proportions such that the MgO content is 6% by mass or more and 15% by mass or less, the CaO content is 13% by mass or more and 16% by mass or less, and the R2O content is 1% by mass or less, where the R2O content represents the total content of Li2O, Na2O, and K2O. Relative to 100 parts by mass of the polyphenylene sulfide resin (A), the glass fiber (B) is in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass.

2. The polyarylene sulfide resin composition according to claim 1, wherein, In the polyphenylene sulfide resin (A), glass fiber (B), and silane coupling agent (C), a thermoplastic elastomer (D) is further compounded as an essential component. Relative to 100 parts by mass of the polyphenylene sulfide resin (A), the thermoplastic elastomer (D) is in the range of 1 to 20 parts by mass.

3. The polyphenylene sulfide resin composition according to claim 1 or 2, which is a melt-kneaded product.

4. A molded article formed by molding the polyphenylene sulfide resin composition according to any one of claims 1 to 3.

5. A method for manufacturing a polyarylene sulfide resin composition, characterized in that, It has a step of compounding polyphenylene sulfide resin (A), glass fiber (B), and silane coupling agent (C) as essential components and melt-kneading in a temperature range above the melting point of the polyphenylene sulfide resin (A). The glass fiber (B) is a glass fiber containing MgO, CaO, and R2O in proportions such that the MgO content is 6% by mass or more and 15% by mass or less, the CaO content is 13% by mass or more and 16% by mass or less, and the R2O content is 1% by mass or less, where the R2O content represents the total content of Li2O, Na2O, and K2O. Relative to 100 parts by mass of the polyphenylene sulfide resin (A), the glass fiber (B) is in the range of 10 to 100 parts by mass, and the silane coupling agent (C) is in the range of 0.01 to 10 parts by mass.

6. The production method of the polyarylene sulfide resin composition according to claim 5, wherein, In the polyphenylene sulfide resin (A), glass fiber (B), and silane coupling agent (C), a thermoplastic elastomer (D) is further compounded as an essential component. Relative to 100 parts by mass of the polyphenylene sulfide resin (A), the thermoplastic elastomer (D) is in the range of 1 to 20 parts by mass.

7. A method for manufacturing a molded article, which has a step of manufacturing a polyphenylene sulfide resin composition by the manufacturing method according to claim 5 or 6; and a step of melt-molding the obtained polyphenylene sulfide resin composition.

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