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 that can suppress 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 blending, 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 with respect to 100 parts by mass of the PAS resin; in the glass fiber, ZrO 2 is contained in an amount of 16% by mass or more, TiO 2 is contained in an amount of 5 to 10% by mass or less, and CaO is contained in a ratio of 0.1 to 5% by mass, and ZrO 2 , TiO 2 and CaO.

Description

Technical Field

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

[0002] Polyphenylene sulfide resin (hereinafter referred to as "PPS resin") is a representative polyarylene sulfide resin (hereinafter referred to as "PAS resin"), which has excellent heat resistance and chemical resistance, and is widely used in automobile parts, electrical and electronic parts, water heater parts, etc. In these applications, most of them require mechanical strength to replace metals and are used as glass fiber reinforced resin compositions. However, although PPS resin itself shows excellent heat resistance and chemical resistance, in applications where it comes into contact with hot water, acidic or alkaline chemicals, the strength of the resin composition is greatly reduced, and its use is limited.

[0003] For this purpose, a mixture containing 5 to 40 weight percent ZrO is provided. 2 A PPS resin composition of glass fiber as a glass having excellent acid resistance and alkali resistance (see Patent Document 1); a B 2 O 3 A PPS resin composition containing glass fibers at a content of 1% by weight or less (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 literature

[0006] Patent Literature

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

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

[0009] Patent Document 3: Japanese Patent Application Publication No. 2001-115020 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] However, these methods use glass fibers with a large amount of alkali components, and therefore the mechanical strength is significantly reduced in a hot water atmosphere and in an acidic state. When a polysiloxane compound is contained, the polysiloxane compound is eluted, resulting in a reduction in durability.

[0012] Therefore, the problem to be solved by the present invention is to provide 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 in an acidic state, a PAS resin composition capable of providing the molded article, and a method for producing the same.

[0013] Solutions for solving problems

[0014] The present inventors have conducted intensive studies to solve the above problems and have found that the use of glass fibers containing specific components can suppress the reduction in mechanical strength of a PAS resin molded product containing a PAS resin and glass fibers in a hot water atmosphere and in an acidic environment, thereby completing the present invention.

[0015] That is, the present invention relates to a polyarylene sulfide resin composition, characterized in that polyarylene sulfide resin (A), glass fiber (B) and silane coupling agent (C) are mixed as essential components.

[0016] Glass fiber (B) is a glass fiber with ZrO 2 Content 16 mass% or more, TiO 2 The content is 5 to 10% by mass or less and the CaO content is 0.1 to 5% by mass. 2 、TiO 2 and CaO glass fibers,

[0017] The amount of the glass fiber (B) is in the range of 10 to 100 parts by mass, and the amount of the silane-silane coupling agent (C) is in the range of 0.01 to 10 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin (A).

[0018] Furthermore, the present invention relates to a molded article obtained by molding the above-described polyarylene sulfide resin composition.

[0019] The present invention also relates to a method for producing a polyarylene sulfide resin composition, characterized in that the polyarylene sulfide resin (A), glass fiber (B) and silane coupling agent (C) are blended as essential components, and melt-kneading is performed at a temperature range of not less than the melting point of the polyarylene sulfide resin (A).

[0020] Glass fiber (B) is a glass fiber with ZrO 2 Content 16 mass% or more, TiO 2 The content is 5 to 10% by mass or less and the CaO content is 0.1 to 5% by mass. 2 、TiO 2 and CaO glass fibers,

[0021] The amount of the glass fiber (B) is in the range of 10 to 100 parts by mass, and the amount of the silane-silane coupling agent (C) is in the range of 0.01 to 10 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin (A).

[0022] The present invention also relates to a method for producing a molded article, comprising the steps of producing a polyarylene sulfide resin composition by the above-described production method; and 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 fibers and capable of suppressing a decrease in mechanical strength even in a hot water atmosphere and in an acidic state, a PAS resin composition capable of providing the molded article, and a method for producing the same. DETAILED DESCRIPTION

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

[0026] Glass fiber (B) is a glass fiber with ZrO 2 Content 16 mass% or more, TiO 2 The content is 5 to 10% by mass or less and the CaO content is 0.1 to 5% by mass. 2 、TiO 2 and CaO glass fibers,

[0027] The amount of the glass fiber (B) is 10 to 100 parts by mass, and the amount of the silane coupling agent (C) is 0.01 to 10 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin (A).

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

[0029]

[0030] (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.)

[0031]

[0032] 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 other structural parts.

[0033] Here, among the structural parts represented by the general formula (1), R in the formula is 1 and R 2 A hydrogen atom is preferred, 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).

[0034]

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

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

[0037]

[0038] In particular, in the present invention, from the viewpoint of heat resistance and mechanical strength of the PAS resin (A), the structural parts represented by the general formulae (5) to (8) are preferably 10 mol% or less. When the PAS resin (A) contains the structural parts represented by the general formulae (5) to (8), the bonding form thereof is any of a random copolymer and a block copolymer.

[0039] The PAS resin (A) 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.

[0040] In addition, the physical properties of the PAS resin (A) are not particularly limited unless the effects of the present invention are impaired, 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 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. However, the melt viscosity (V6) was measured using a rheometer, CFT-500D manufactured by Shimadzu Corporation, at 300°C and a load of 1.96×10 6 After the PAS resin (A) was kept at Pa, L / D = 10 (mm) / 1 (mm) for 6 minutes, the measured value of the melt viscosity was taken.

[0043] (Non-Newtonian index)

[0044] The non-Newtonian index of the PAS resin (A) used in the present invention 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, 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 wear 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 using a capillary rheometer at a melting point of +20°C, a ratio of pore length (L) to pore diameter (D) of L / D=40, shear rate (SR) and shear stress (SS). The closer the non-Newtonian index (N value) is to 1, the closer it is to a linear structure, and the higher the non-Newtonian index (N value), the greater the structural divergence.

[0045] SR=K·SS N

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

[0047] (Manufacturing method)

[0048] The method for producing the PAS resin (A) is not particularly limited, and examples thereof include (production method 1) a method of adding a dihalogenated aromatic compound in the presence of sulfur and sodium carbonate, adding a polyhalogenated aromatic compound or other copolymerization components as needed, and polymerizing the compound; (production method 2) a method of adding a dihalogenated aromatic compound in the presence of a thioetherifying agent, etc., adding a polyhalogenated aromatic compound or other copolymerization components as needed, and polymerizing the compound; (production method 3) a method of adding other copolymerization components as needed to self-condense parachlorothiophenol; (production method 4) a method of 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 or amino groups, etc. Among these methods, the method of (production method 2) is universal and therefore preferred. During the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid, or an alkali metal hydroxide may be added to adjust the degree of polymerization. Among the above-mentioned methods (production method 2), the polyarylene sulfide resin is particularly preferably obtained by the following method: a water-containing thioetherification agent is introduced into a heated mixture containing an organic polar solvent and a dihalogenated aromatic compound at a rate that can remove water from the reaction mixture, the dihalogenated aromatic compound and the thioetherification agent, and if necessary, a polyhalogenated aromatic compound are added to the organic polar solvent, and the reaction is carried out, and the water content in the reaction system is controlled to be in the range of 0.02 mol to 0.5 mol relative to 1 mol of the organic polar solvent (see Japanese Patent Application Laid-Open No. 07-07-07, 2004). 228699 Gazette); a method for carrying out a reaction by adding a dihalogenated aromatic compound and, if necessary, a polyhalogenated aromatic compound or other copolymerization components in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, controlling the amount of the alkali metal hydrosulfide and the organic acid alkali metal salt to be in the range of 0.01 mol to 0.9 mol relative to 1 mol of the sulfur source, and controlling the water content in the reaction system to be in the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent (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. are mentioned. In addition, the halogen atoms contained in each of the above compounds are preferably chlorine atoms and bromine atoms.

[0049] The post-treatment method of the reaction mixture containing the PAS resin (A) obtained by the polymerization step is not particularly limited, and examples thereof include: (Post-treatment 1) After the polymerization reaction is completed, the reaction mixture is first subjected to distillation under reduced pressure or normal pressure to remove the solvent directly or after adding an acid or a base, 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 for the low molecular weight polymer), acetone, methyl ethyl ketone, alcohols, etc., 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 (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 , allowing solid products such as PAS and inorganic salts to settle, filtering out, washing and drying these precipitates; or (post-treatment 3) after the polymerization reaction is completed, adding a reaction solvent (or an organic solvent with an equivalent solubility for low molecular weight polymers) to the reaction mixture and stirring, filtering out the low molecular weight polymers, washing with water, acetone, methyl ethyl ketone, alcohols and other solvents once or twice or more, and then neutralizing, washing with water, filtering and drying; (post-treatment 4) after the polymerization reaction is completed, adding water to the reaction mixture for water washing and filtering, adding acid to the water washing as needed for acid treatment, and drying; (5) after the polymerization reaction is completed, filtering the reaction mixture, washing with a reaction solvent once or twice or more as needed, and further washing with water, filtering and drying, etc.

[0050] In the post-treatment methods exemplified in (Post-treatment 1) to (Post-treatment 5) above, the drying of the PAS resin (A) may be performed in a vacuum or in an inert gas atmosphere such as air or nitrogen.

[0051] The PAS resin composition of the present invention is prepared by mixing glass fiber (B) as an essential component. The glass fiber (B) is a glass fiber containing ZrO 2 Content 16 mass% or more, TiO 2 The content is 5 to 10% by mass or less and the CaO content is 0.1 to 5% by mass. 2 、TiO 2 and CaO glass fibers.

[0052] ZrO in glass fiber 2 The content is 16 mass % or more, more preferably 18 mass % or more, and the upper limit is not specified, preferably 25 mass % or less, and more preferably 24 mass % or less. 2 The content may be greater than 0% by mass, preferably 0.1% by mass or more, more preferably 5% by mass or more, and 10% by mass or less, preferably 9% by mass or less. In addition, the CaO content in the glass fiber is 0.1% by mass or more, preferably 1% by mass or more, and 5% by mass or less, preferably 4% by mass or less. By making the ZrO in the glass fiber 2 Content, TiO 2 When the content of Al and CaO is within this range, the dissolution of glass components in acidic, alkaline, and humid and hot environments can be suppressed, while achieving a balance between chemical resistance and mechanical strength.

[0053] Furthermore, the glass fiber may optionally contain R 2 O(where R 2 O is LiO 2 、Na 2 O and K 2 O general term. ) R in glass fiber 2 O content (wherein, represents LiO 2 、Na 2 O and K 2 The total content of aluminum oxide (AAO) is arbitrary and not particularly limited, but is preferably 10% by mass or more and preferably 30% by mass or less. By setting it within this range, the acid resistance is further improved. Furthermore, the glass fiber may optionally contain aluminum oxide (Al 2 O 3), the alumina content in the glass fiber is arbitrary and not particularly limited, preferably below 5 mass %, more preferably below 2 mass %, the lower limit is not limited and may not exist, preferably above 0 mass %, more preferably greater than 0 mass %.

[0054] The balance contains silicon oxide (SiO 2 ). Silicon oxide (SiO 2 ) content is not particularly limited as long as it is the remainder of the above-mentioned components, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and is preferably 50% by mass or more, more preferably 54% by mass or more in the glass fiber.

[0055] By blending these glass fibers (B), a molded product excellent in moist heat resistance, acid resistance, alkali resistance and mechanical strength can be obtained.

[0056] The amount of the glass fiber (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 30 parts by mass or more relative to 100 parts by mass of the PAS resin (A), and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less. By setting the amount of the glass fiber (B) to be within this range, a molded product having excellent moisture and heat resistance, acid resistance, alkali resistance, and mechanical strength can be obtained.

[0057] The PAS resin composition of the present invention is compounded with a silane coupling agent (C) as an essential component. The silane coupling agent (C) used in the present invention is not particularly limited as long as the effect of the present invention is not impaired. It is preferably a silane coupling agent having a functional group that reacts with a carboxyl group, and examples thereof include silane coupling agents having an epoxy group, an isocyanate group, an amino group, or a hydroxyl group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylethyl Isocyanate alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc.; Aminoalkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane; Hydroxylalkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. In the present invention, the silane coupling agent (C) is not an essential component, but when blending, as long as the effect of the present invention is not impaired, the amount thereof is not particularly limited, and relative to 100 parts by mass of PAS resin (A), the blending amount thereof 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, and more preferably 5 parts by mass or less. Within this range, a molded product having excellent moisture and heat resistance, acid resistance, alkali resistance and mechanical strength can be obtained.

[0058] The PAS resin composition of the present invention can be mixed with a thermoplastic elastomer (D) as an arbitrary component. As the thermoplastic elastomer, polyolefin elastomers, fluorine-based elastomers or silicone-based elastomers can be cited, wherein polyolefin elastomers are preferred. Relative to 100 parts by mass of 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, and more preferably 15 parts by mass or less. Within this range, a molded product having excellent moisture and heat resistance, acid resistance, alkali resistance and mechanical strength, particularly impact resistance can be obtained.

[0059] For example, the polyolefin elastomer may include an α-olefin homopolymer, 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, the α-olefin may include ethylene, propylene, 1-butene, and other α-olefins having a carbon number of 2 to 8. In addition, the functional group may 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 above-mentioned 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; α,β-unsaturated carboxylic acid metal salts such as ionomers (as metals, alkali metals such as sodium, alkaline earth metals such as calcium, and zinc, etc., can be cited); α,β-unsaturated carboxylic acid glycidyl esters such as glycidyl methacrylate; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and derivatives (monoesters, diesters, and anhydrides) of the above-mentioned α,β-unsaturated dicarboxylic acids, etc., one or more of the above-mentioned thermoplastic elastomers can be used alone or in combination of two or more.

[0060] In the present invention, a fibrous filler other than the glass fiber (B) as the essential component (hereinafter also referred to as "other fibrous filler") may be blended as an optional component. Examples of such other fibrous fillers include glass fibers other than the glass fiber (B), carbon fibers, silane glass fibers, ceramic fibers, aromatic polyamide fibers, metal fibers, and the like, and one or more of them may be blended.

[0061] Although it is an optional component, when compounding, the compounding amount of the fibrous filler is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 15 parts by mass or more, and is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). By setting the compounding amount of the fibrous filler within these ranges, a better effect can be obtained in terms of maintaining the mechanical strength of the molded product.

[0062] The fibrous filler material may be a material processed by a surface treatment agent or a sizing agent. This is preferred because the bonding strength with the PAS resin (A) can be improved. Examples of the surface treatment agent or sizing agent include 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, epoxy, isocyanate, and vinyl.

[0063] The PAS resin composition of the present invention may further include the glass fiber (B) as an essential component and other fillers (hereinafter, also referred to as "other fillers") other than other fibrous fillers as an optional component as required. As these other fillers, known and commonly used materials may be used as long as the effects of the present invention are not impaired, and for example, fillers in various shapes such as granular or plate-like shapes may be cited. In addition, non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, glass beads, zeolite, ground fiber, and calcium sulfate may also be used.

[0064] In the present invention, other fillers are not essential components, but during compounding, as long as the effect of the present invention is not damaged, its compounding amount is not particularly limited. As the compounding amount of other fillers, for example, relative to 100 mass parts of PAS resin (A), it is preferably more than 1 mass part, more preferably more than 10 mass parts, preferably less than 600 mass parts, more preferably less than 200 mass parts. Within this range, resin combination shows good mechanical strength and moldability, so it is preferred.

[0065] Furthermore, the PAS resin composition of the present invention may also appropriately select, in addition to the above-mentioned components, polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyetherketone resins, polyarylene resins, polyethylene resins, polypropylene resins, polytetrafluoroethylene resins, polyvinylidene fluoride resins, polystyrene resins, ABS resins, phenolic resins, polyurethane resins, liquid crystal polymers and other synthetic resins (hereinafter referred to as synthetic resins) as arbitrary components according to the purpose. In the present invention, the above-mentioned synthetic resins are not essential components, but 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 invention, for example, the range of 5 parts by mass or more and the range of 15 parts by mass or less can be cited relative to 100 parts by mass of the PAS resin (A). In other words, the ratio of the PAS resin (A) 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.

[0066] In addition, the PAS resin composition of the present invention may also contain 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) as required, which are mixed as arbitrary components. These additives are not essential components, and are preferably in the range of 0.01 parts by mass or more, and preferably in the range of 1000 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, for the purpose of not impairing the effects of the present invention and according to the application.

[0067] The method for producing a polyarylene sulfide resin composition of the present invention is characterized in that it comprises the steps of blending a polyarylene sulfide resin (A), a glass fiber (B) and a silane coupling agent (C) as essential components, and melt-kneading the mixture at a temperature not lower than the melting point of the polyarylene sulfide resin (A);

[0068] Glass fiber (B) is a glass fiber with ZrO 2 Content 16 mass% or more, TiO 2 The content is 5 to 10% by mass or less and the CaO content is 0.1 to 5% by mass. 2 、TiO 2 and CaO glass fibers,

[0069] The amount of the glass fiber (B) is in the range of 10 to 100 parts by mass, and the amount of the silane-silane coupling agent (C) is in the range of 0.01 to 10 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin (A).

[0070] The following is a detailed description.

[0071] The method for producing the PAS resin composition of the present invention comprises the step of blending the above-mentioned essential components and performing melt kneading in a temperature range above the melting point of the PAS resin (A). In more detail, the PAS resin composition of the present invention is blended by each essential component and other optional components as required. There is no particular limitation on the method for producing the resin composition used in the present invention, and a method of blending the essential components and the optional components as required and performing melt kneading can be cited. In more detail, a method of uniformly performing dry mixing with a rotary drum or a Henschel mixer as required, and then putting it into a twin-screw extruder for melt kneading can be cited.

[0072] Melt kneading can be carried out by heating the resin temperature to a temperature range above the melting point of the PAS resin (A), preferably a temperature range above the melting point + 10°C, more preferably above the melting point + 10°C, further preferably above the melting point + 20°C, preferably below the melting point + 100°C, more preferably below the melting point + 50°C.

[0073] As the above-mentioned melt kneading machine, 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 discharge 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). It is further preferred to perform melt kneading under the condition that their ratio (discharge amount / screw speed) is in the range of 0.02 to 5 (kg / hr / rpm). In addition, the addition and mixing of each component to the melt kneading machine can be performed simultaneously or in batches. For example, when adding the glass fiber (B) as an essential component and other fibrous fillers as required to the above-mentioned components, it is preferred to feed them into the extruder from the side feeder of the above-mentioned twin-screw kneading extruder from the viewpoint of dispersibility. For the position of the side feeder, the ratio of the distance from the resin input part (top feeder) of the extruder to the side feeder relative to the total length of the screw of the above-mentioned twin-screw kneading extruder is preferably 0.1 or more, more preferably 0.3 or more. Furthermore, the ratio is preferably 0.9 or less, and more preferably 0.7 or less.

[0074] The PAS resin composition of the present invention obtained by melt kneading is a molten mixture containing the above-mentioned essential components, as well as optional components added as needed and components derived therefrom. Therefore, the PAS resin (A) of the PAS resin composition of the present invention forms a continuous phase, and has a form in which other essential components and optional components are dispersed. After the melt kneading, the PAS resin composition of the present invention is preferably pre-dried at a temperature range of 100 to 150° C. by a known method, such as extruding the molten resin composition into a linear shape, and then processed into a form such as pellets, sheets, granules, powders, etc. as needed.

[0075] The molded product of the present invention is formed by melt-molding the PAS resin composition. In addition, the method for manufacturing the molded product of the present invention has a step of melt-molding the above-mentioned PAS resin composition. Therefore, the PAS resin (A) of the molded product of the present invention forms a continuous phase and has a form in which other essential components and optional components other than the PAS resin (A) are dispersed. By having such a form, the PAS resin composition can obtain a molded product with excellent moisture and heat resistance, acid resistance, alkali resistance and mechanical strength.

[0076] The PAS resin composition of the present invention can be used for various moldings such as injection molding, compression molding, extrusion molding of composite materials, sheets, tubes, etc., drawing molding, blow molding, transfer molding, etc., but the demolding property is particularly excellent, so it is suitable for injection molding. When 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 above-mentioned PAS resin composition is melted at a resin temperature in a temperature range above the melting point of the PAS resin (A), preferably a temperature range above the melting point + 10°C, more preferably a temperature range of melting point + 10°C to melting point + 100°C, and further preferably a melting point + 20°C to melting point + 50°C, the resin extrusion port is used to inject it into the mold for molding. At this time, the mold temperature is also set to a known temperature range, such as room temperature (23°C) to 300°C, preferably set to 120 to 180°C.

[0077] As the products of the molded articles of the PAS resin composition of the present invention, for example, pipes, liners, cap nuts, pipe joints, (elbows, headers, T-tubes, reducers, joints, couplers, etc.), various valves, flow meters, gaskets (seals, closed types) and other pipes for conveying fluids and various parts attached to the pipes (also referred to as "fluid conveying parts" in the present invention) can be cited. Therefore, for example, various pipes related to fuel / exhaust system / intake system, air intake nozzles, intake manifolds, fuel pumps, engine cooling water joints, water outlets and other parts attached to internal combustion engines such as automobile parts can be cited, and can also be applied to various other purposes. Furthermore, examples can also be given of heat dissipation parts for engine control units of automobiles, or heat dissipation parts for motors, heat dissipation parts for LED substrates, radiators for various electrical / electronic equipment substrates, etc. In addition, the molded articles of the present invention can be made not only into heat dissipation parts, but also into the following common resin molded articles.Examples include protection / support components for box-type electrical / electronic component integrated modules / multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay boxes, switches, coil frames, capacitors, varistor boxes, optical pickups, vibrators, mutual inductors, plugs, printed circuit boards, tuners, microphones, headphones, small motors, head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD slides, FDD brackets, motor brush holders, parabolic antennas, computer-related components, etc.; electrical / electronic components represented by VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, / laser discs / laser records / DVD discs / blue-ray discs and other audio / video equipment parts, lighting parts, refrigerator parts, air conditioning parts, typewriter parts, word processor parts, or water heaters, bathtub hot water, temperature sensors and other water-using equipment parts, etc., represented by household and office electrical product parts; office computer related parts, telephone related parts, fax related parts, copier related parts, cleaning fixtures, motor parts, lighters, typewriters, etc., represented by optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, watches, etc.; alternator terminal wire (alternator terminal), alternator connector, brush holder, collector ring, IC regulator, dimmer potentiometer base, relay block, circuit breaker, exhaust valve and other valves, fuel / exhaust / intake pipes, intake nozzle breather pipe, intake manifold, fuel pump, engine cooling water joint, carburetor body, carburetor gasket, exhaust sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor sensor), crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine blade, wiper motor related parts, distributor, starter switch, ignition coil and its coil frame, motor insulator, motor rotor, motor core, starter relay, transmission wiring harness, window washer nozzle, air conditioner panel switch substrate, fuel related solenoid valve coil, fuse connector, speaker terminal, electronic control component insulation board, stepping motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid coil frame, oil filter, ignition device housing, power module, inverter, power device, intelligent power module, insulated gate bipolar transistor, power control unit, reactor, torque converter, capacitor, insulator, motor terminal block, battery, electric compressor, battery current sensor, junction box, DLI system ignition coil storage housing and other automobile / vehicle related parts, and other various uses.

[0078] Example

[0079] 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, in the following, "%" or "part" is based on mass unless otherwise specified.

[0080] <Examples 1 to 5 and Comparative Examples 1 to 3>

[0081] According to the composition and compounding amount recorded in Table 1, each material is mixed with 0.8 parts by mass of polyolefin wax (high-density polyethylene wax "Luwax AH-6" manufactured by BASF). Then, these compounding materials are put into the twin-screw extruder "TEX-30α (product name)" with vents manufactured by Nippon Steel Works, Ltd., with a resin component discharge of 30 kg / hr and a screw speed of 200 rpm. The resin is melt-kneaded at a set resin temperature of 320°C to obtain pellets of the resin composition. Glass fiber is fed from a side feeder, and the other materials are pre-mixed evenly with a rotary drum and fed from a top feeder. After drying the pellets of the obtained resin composition in a gear oven at 140°C for 2 hours, various test pieces are made by injection molding, and the following tests are carried out.

[0082] <Tensile Strength>

[0083] 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 molding was performed using 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 in order to make a test piece without a welded portion, the resin was injected from a single gate of the ISO D2 sheet. The tensile strength of the obtained dumbbell was measured using the measurement method according to ISO 527-1 and 2.

[0084] <Flexural Strength, Flexural Modulus>

[0085] The flexural strength and flexural modulus of the ISO TYPE-A dumbbell plates were measured by the measurement method in accordance with ISO 178.

[0086] <Impact Strength>

[0087] The center of the dumbbell-shaped test piece for tensile test was cut into a rod with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. After cutting, the impact resistance test piece was made. The Charpy impact test was carried out according to ISO 179-1 / 1eA to measure the impact strength (kJ / mm 2 ) determination.

[0088] <Linear thermal expansion coefficient>

[0089] The central part of the dumbbell-shaped test piece for tensile test was cut into a rectangular parallelepiped with a length of 10 mm, a width of 10 mm, and a thickness of 4 mm. This was used as a linear thermal expansion coefficient test piece. The linear thermal expansion coefficient parallel to the flow direction in the measurement temperature range of -50 to 50°C was measured in accordance with ISO 11359-2.

[0090] <Acid resistance test>

[0091] Method A: After immersion in 46% hydrofluoric acid (special grade reagent manufactured by Fuji Film & Wako Pure Chemical Industries, Ltd.) at room temperature for 100 hours, the tensile strength was measured. The retention rate was calculated by dividing the tensile strength of the material before immersion. The results are shown in Tables 1 and 2.

[0092] Method B: After immersion in Sanpoll stock solution (9.5% hydrochloric acid, containing surfactant (alkyl trimethyl ammonium) manufactured by Dainippon Pyrethrum Co., Ltd.) at room temperature for 500 hours, the tensile strength was measured. Furthermore, the retention rate was calculated by dividing the tensile strength of the material before immersion. The results are shown in Tables 1 and 2.

[0093] <Alkali resistance test>

[0094] Method C: After immersion in Domestos Disinfectant Cleaner stock solution (made by Unilever Japan KK, 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, the tensile strength is measured. Then, the retention rate is calculated by dividing the tensile strength of the material before immersion. The results are shown in Tables 1 and 2.

[0095] <Moisture and heat resistance test>

[0096] The D method was used to perform a 100-hour pressure cooking test at 95°C, 95% humidity, and 2 atmospheres to measure the tensile strength. The tensile strength was then divided by the tensile strength of the material before the test to calculate the retention rate (%). The results are shown in Tables 1 and 2.

[0097] [Table 1]

[0098] Example 1 Example 2 Example 3 Example 4 A1 100 100 - - A2 - - 100 - A3 - - - 100 A4 - - - - B1 67.6 46.7 67.6 67.6 B2 - - - - C1 0.5 0.5 0.5 0.5 D1 - 7.8 - - Tensile Strength MPa 170 138 171 167 Bending Strength MPa 240 208 243 238 Flexural modulus GPa 14.8 9.4 14.8 15.0 Impact strength <![CDATA[kJ / m 2 ]]> 8.3 12.9 8.6 8.1 Linear thermal expansion coefficient <![CDATA[×10 -6 / K]]> 15.8 17.8 16.1 15.6 A tensile strength MPa 161 134 163 162 Retention rate ％ 95％ 97％ 95％ 97％ B method tensile strength MPa 169 138 168 165 Retention rate ％ 99％ 100％ 98％ 99％ C method tensile strength MPa 168 137 167 165 Retention rate ％ 99％ 99％ 98％ 99％ D tensile strength MPa 168 137 167 164 Retention rate ％ 99％ 99％ 98％ 98％

[0099] [Table 2]

[0100] Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 A1 - 100 100 100 A2 - - - - A3 - - - - A4 100 - - - B1 67.6 - - - B2 - 67.6 46.7 B3 - - - 67.6 C1 0.5 0.5 0.5 0.5 D1 - - 7.8 - Tensile Strength MPa 161 192 151 168 Bending Strength MPa 230 276 230 236 Flexural modulus GPa 14.2 15.5 9.5 14.5 Impact strength <![CDATA[kJ / m 2 ]]> 8.1 9.5 13.5 8.1 Linear thermal expansion coefficient <![CDATA[×10 -6 / K]]> 16.2 13.2 15.1 16.0 A tensile strength MPa 154 152 127 153 Retention rate ％ 96％ 79％ 84％ 91％ B method tensile strength MPa 160 180 144 162 Retention rate ％ 99％ 94％ 95％ 96％ C method tensile strength MPa 155 176 140 159 Retention rate ％ 96％ 92％ 93％ 95％ D tensile strength MPa 154 190 149 162 Retention rate ％ 96％ 99％ 99％ 96％

[0101] In addition, the compounding ratio of the compounding component in Table 1 and 2 shows a mass part, and the following were used.

[0102] PAS resin ingredients

[0103] Polyphenylene sulfide resin

[0104] A1: melt viscosity 56 Pa·s, non-Newtonian index 1.07

[0105] A2: melt viscosity 180 Pa·s, non-Newtonian index 1.07

[0106] A3: melt viscosity 7 Pa·s, non-Newtonian index 1.07

[0107] A4: melt viscosity 700 Pa·s, non-Newtonian index 1.60

[0108] (Manufacturing Example 1) Manufacture of polyphenylene sulfide resin (A1)

[0109] [Process 1]

[0110] In a 150-liter autoclave with stirring blades connected to a pressure gauge, a thermometer, a condenser, a decanter, and a distillation tower, 33.075 parts by mass (225 molar parts) of p-dichlorobenzene (hereinafter referred to as "p-DCB"), 3.420 parts by mass (34.5 molar parts) of NMP, 27.300 parts by mass of a 47.23% by mass NaSH aqueous solution (230 molar parts as NaSH), and 18.533 parts by mass of a 49.21% by mass NaOH aqueous solution (228 molar parts as NaOH) were added, and the temperature was raised to 173° C. in a nitrogen atmosphere for 5 hours while stirring. After 27.300 parts by mass of water was distilled off, 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. After the dehydration was completed, the autoclave was in a state where the anhydrous sodium sulfide composition in the form of microparticles was dispersed in the p-DCB. The NMP content in the composition was 0.079 parts by mass (0.8 parts by mole), indicating that 98 mol% (33.7 parts by mole) of the NMP charged was hydrolyzed into the sodium salt of the NMP ring-opening product (4-(methylamino)butyric acid) (hereinafter referred to 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. All of the NaSH and NaOH charged were converted into anhydrous Na 2 The theoretical dehydration amount at S is 27.921 parts by mass, which means that 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) are consumed by the hydrolysis reaction of NMP and NaOH and do not exist in the autoclave as water, and the remaining 0.269 parts by mass (14.9 parts by mole) remain in the autoclave as water or crystal water. The amount of water in the autoclave is 0.065 mol per 1 mol of sulfur atoms present in the autoclave.

[0111] [Process 2]

[0112] After the above dehydration process is completed, the internal temperature is cooled to 160°C, 46.343 parts by mass (467.5 parts by mole) of NMP is added, and the temperature is raised to 185°C. The amount of water in the autoclave is 0.025 mol relative to 1 mol of NMP added in step 2. When the gauge pressure reaches 0.00 MPa, the valve connected to the distillation tower is opened, and the temperature is raised to an internal temperature of 200°C in 1 hour. At this time, the cooling and valve opening are controlled so that the outlet temperature of the distillation tower is below 110°C. The mixed vapor of p-DCB and water distilled out is condensed by a condenser, separated by a decanter, and p-DCB is returned to the autoclave. The amount of distilled water is 0.228 parts by mass (12.7 parts by mole).

[0113] [Process 3]

[0114] At the beginning of step 3, the amount of water in the autoclave was 0.041 parts by mass (2.3 parts by mole), which was 0.005 parts by mass relative to 1 part of NMP added in step 2, and 0.010 parts by mass relative to 1 part 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 parts by mass relative to 1 part of sulfur atoms present in the autoclave. Next, the temperature was raised from 200°C to 230°C in 3 hours, and after stirring at 230°C for 1 hour, the temperature was raised to 250°C and stirred for 1 hour. The gauge pressure was 0.03MPa at an internal temperature of 200°C, and the final gauge pressure was 0.40MPa. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the obtained slurry, and after stirring at 80°C for 1 hour, it was filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed and filtered. This operation was repeated 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 filter. Stir the filter cake with 3 parts by mass (3 liters) of warm water for 1 hour, wash and filter. Repeat this operation twice. Use a hot air dryer to dry at 120°C overnight to obtain a white powdery PPS resin (A1). The melt viscosity of the polymer at 300°C is 56 Pa·s. The non-Newtonian index is 1.07.

[0115] (Manufacturing Example 2) Manufacture of polyphenylene sulfide resin (A2)

[0116] [Process 1]

[0117] In a 150-liter autoclave with stirring blades connected to a pressure gauge, a thermometer, a capacitor, a decanter, and a distillation tower, 33.222 parts by mass of p-DCB (226 parts by mole), 3.420 parts by mass of NMP (34.5 parts by mole), 27.300 parts by mass of a 47.23% by mass NaSH aqueous solution (230 parts by mole as NaSH), and 18.533 parts by mass of a 49.21% by mass NaOH aqueous solution (228 parts by mole as NaOH) were added, and the temperature was raised to 173° C. in a nitrogen atmosphere for 5 hours while stirring. After 27.300 parts by mass of water were distilled off, 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. After the dehydration was completed, the autoclave was in a state where the particulate anhydrous sodium sulfide composition was dispersed in the p-DCB. The NMP content in the composition was 0.079 parts by mass (0.8 parts by mole), indicating that 98 mol% (33.7 parts by mole) of the NMP charged was hydrolyzed into SMAB, a ring-opened form of NMP. The amount of SMAB in the autoclave was 0.147 parts by mole per 1 mole of sulfur atoms present in the autoclave. All of the NaSH and NaOH charged were converted into anhydrous Na 2 The theoretical dehydration amount at S is 27.921 parts by mass, which means that 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) are consumed by the hydrolysis reaction of NMP and NaOH and do not exist in the autoclave as water, and the remaining 0.269 parts by mass (14.9 parts by mole) remain in the autoclave as water or crystal water. The amount of water in the autoclave is 0.065 mol per 1 mol of sulfur atoms present in the autoclave.

[0118] [Process 2]

[0119] After the above dehydration process is completed, the internal temperature is cooled to 160°C, 46.343 parts by mass (467.5 parts by mole) of NMP is added, and the temperature is raised to 185°C. The amount of water in the autoclave is 0.025 mol relative to 1 mol of NMP added in step 2. When the gauge pressure reaches 0.00 MPa, the valve connected to the distillation tower is opened, and the temperature is raised to an internal temperature of 200°C in 1 hour. At this time, the cooling and valve opening are controlled so that the outlet temperature of the distillation tower is below 110°C. The mixed vapor of p-DCB and water distilled out is condensed by a condenser, separated by a decanter, and p-DCB is returned to the autoclave. The amount of distilled water is 0.228 parts by mass (12.7 parts by mole).

[0120] [Process 3]

[0121] At the beginning of step 3, the amount of water in the autoclave was 0.041 parts by mass (2.3 parts by mole), which was 0.005 parts by mass relative to 1 part of NMP added in step 2, and 0.010 parts by mass relative to 1 part 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 parts by mass relative to 1 part of sulfur atoms present in the autoclave. Next, the internal temperature was raised from 200°C to 230°C over 3 hours, and after stirring at 230°C for 3 hours, the temperature was raised to 250°C and stirred for 1 hour. The gauge pressure was 0.03MPa at an internal temperature of 200°C, and the final gauge pressure was 0.40MPa. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the obtained slurry, and after stirring at 80°C for 1 hour, it was filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed and filtered. This operation was repeated 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 filter. Stir the filter cake with 3 parts by mass (3 liters) of warm water for 1 hour, wash and filter. Repeat this operation twice. Use a hot air dryer to dry at 120°C overnight to obtain a white powdery PPS resin (A2). The melt viscosity of the polymer at 300°C is 180 Pa·s. The non-Newtonian index is 1.07.

[0122] (Manufacturing Example 3) Manufacture of polyphenylene sulfide resin (A3)

[0123] [Process 1]

[0124] In a 150-liter autoclave with stirring blades connected to a pressure gauge, a thermometer, a capacitor, a decanter, and a distillation tower, 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% by mass NaSH aqueous solution (230 parts by mole as NaSH), and 18.533 parts by mass of a 49.21% by mass NaOH aqueous solution (228 parts by mole as NaOH) were added, and the temperature was raised to 173° C. in a nitrogen atmosphere for 5 hours while stirring. After 27.300 parts by mass of water was distilled off, 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. After the dehydration was completed, the autoclave was in a state where the particulate anhydrous sodium sulfide composition was dispersed in the p-DCB. The NMP content in the composition was 0.079 parts by mass (0.8 parts by mole), indicating that 98 mol% (33.7 parts by mole) of the NMP fed was hydrolyzed into SMAB, a ring-opened form of NMP. The amount of SMAB in the autoclave was 0.147 parts by mole per 1 mole of sulfur atoms present in the autoclave. All of the NaSH and NaOH fed were converted into anhydrous Na 2The theoretical dehydration amount at S is 27.921 parts by mass, which means that 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) are consumed by the hydrolysis reaction of NMP and NaOH and do not exist in the autoclave as water, and the remaining 0.269 parts by mass (14.9 parts by mole) remain in the autoclave as water or crystal water. The amount of water in the autoclave is 0.065 mol per 1 mol of sulfur atoms present in the autoclave.

[0125] [Process 2]

[0126] After the above dehydration process is completed, the internal temperature is cooled to 160°C, and 46.343 parts by mass (467.5 parts by mole) of NMP is heated to 185°C. The amount of water in the autoclave is 0.025 mol relative to 1 mol of NMP added in step 2. When the gauge pressure reaches 0.00 MPa, the valve connected to the distillation tower is opened, and the temperature is raised to 200°C in 1 hour. At this time, the cooling and valve opening are controlled so that the outlet temperature of the distillation tower is below 110°C. The mixed vapor of p-DCB and water distilled out is condensed by a condenser, separated by a decanter, and p-DCB is returned to the autoclave. The amount of distilled water is 0.228 parts by mass (12.7 parts by mole).

[0127] [Process 3]

[0128] At the beginning of step 3, the amount of water in the autoclave was 0.041 parts by mass (2.3 parts by mole), which was 0.005 parts by mass relative to 1 mole of NMP added in step 2, and 0.010 parts by mass 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 parts by mass relative to 1 mole of sulfur atoms present in the autoclave. Next, the temperature was raised from 200°C to 230°C in 3 hours, and after stirring at 230°C for 1 hour, the temperature was raised to 250°C and stirred for 1 hour. The gauge pressure was 0.03MPa at an internal temperature of 200°C, and the final gauge pressure was 0.40MPa. After cooling, 0.650 parts by mass was injected into 3 parts by mass (3 liters) of water in the obtained slurry, and after stirring at 80°C for 1 hour, it was filtered. The filter cake was stirred with 3 parts by mass (3 liters) of warm water for 1 hour, washed and filtered. This operation was repeated 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 filter. Stir the filter cake with 3 parts by mass (3 liters) of warm water for 1 hour, wash and filter. Repeat this operation twice. Use a hot air dryer to dry at 120°C overnight to obtain a white powdery PPS resin (A3). The melt viscosity of the polymer at 300°C is 7 Pa·s. The non-Newtonian index is 1.07.

[0129] (Manufacturing Example 4) Manufacture of polyphenylene sulfide resin (A4)

[0130] In a 150-liter autoclave connected to a pressure gauge, a thermometer, a capacitor, a stirring blade, and a bottom valve, 19.413 parts by mass of sodium sulfide flakes (60.3% by mass Na2S) and 45.000 parts by mass of NMP were added. The temperature was raised to 209°C while stirring under a nitrogen stream, and 4.644 parts by mass of water were distilled out (the amount of residual water was 1.13 mol per mol 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. At a liquid temperature of 150°C, nitrogen was used to pressurize to a gauge pressure of 0.1 MPa and the temperature was started. Stir for 3 hours at a liquid temperature of 260°C and the reaction was allowed to proceed, and the upper part of the autoclave was cooled by sprinkling water. Then, 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 and did not drop. The maximum pressure during the reaction was 0.85 MPa.

[0131] After the reaction, the mixture was cooled. After cooling, 0.650 parts by mass of the mixture was injected into 3 parts by mass (3 liters) of water in the obtained 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 filtered. This operation was repeated 7 times. The mixture was dried overnight at 120°C using a hot air dryer.

[0132] Then, the resulting product was heat treated at 250°C for 3 hours in a hot air dryer to obtain a PPS resin (A4). The melt viscosity of the obtained polymer was 700 Pa·s and the non-Newtonian index was 1.60.

[0133] Fiberglass

[0134] B1: Glass fiber (ZrO 2 Content 17 mass%, TiO 2 content 10 mass%, CaO content 1 mass%, R 2 O content: 17 mass%, SiO 2 Residue), average fiber length 3mm, average fiber diameter 13μm

[0135] B2: E glass "T-717H" manufactured by Nippon Electric Glass Co., Ltd. (MgO content 2.5 wt%, CaO content 20.5 wt%, R 2 O content is less than 1.5wt%, Al 2 O 3 Content 14wt%, SiO 2 is the remainder), average fiber length 3mm, average fiber diameter 10μm.

[0136] B3: Glass fiber (ZrO2 Content 20 mass%, TiO 2 content 2 mass%, CaO content 1 mass%, R 2 O content 17 mass%, SiO 2 is the remainder), average fiber length 3mm, average fiber diameter 13μm.

[0137] Silane coupling agent

[0138] C1: 3-Glycidoxypropyltrimethoxysilane "SH-6040" manufactured by Dow Corning Corporation

[0139] Thermoplastic elastomer

[0140] D1: "BONDFAST 7M" manufactured by Sumitomo Chemical Co., Ltd., containing 67% by mass of ethylene, 6% by mass of glycidyl methacrylate, and 27% by mass of methyl acrylate as copolymer components.

Claims

1. A polyarylene sulfide resin composition, characterized in that, it is a polyarylene sulfide resin composition prepared by compounding polyarylene sulfide resin (A), glass fiber (B) and silane coupling agent (C) as essential components, The glass fiber (B) is a glass fiber containing ZrO 2 in an amount of 16% by mass or more, TiO 2 in an amount of 5 to 10% by mass and CaO in a content ratio of 0.1 to 5% by mass, 2 TiO 2 and CaO. wherein, based on 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.

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

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

4. A molded article, which is formed from the polyarylene 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 polyarylene sulfide resin (A), glass fiber (B) and silane coupling agent (C) as essential components and performing melt-kneading at a temperature range above the melting point of the polyarylene sulfide resin (A), The glass fiber (B) is a glass fiber containing ZrO 2 at a content of 16% by mass or more, TiO 2 at a content of 5 to 10% by mass and a CaO content rate of 0.1 to 5% by mass, and containing ZrO 2 , TiO 2 and CaO. wherein, based on 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.

6. The method for manufacturing a polyarylene sulfide resin composition according to claim 5, wherein, in the polyarylene sulfide resin (A), glass fiber (B) and silane coupling agent (C), a thermoplastic elastomer (D) is further compounded as an essential component, and based on 100 parts by mass of the polyarylene 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 polyarylene sulfide resin composition by the manufacturing method according to claim 4; and a step of melt-molding the obtained polyarylene sulfide resin composition.

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