JP7497568B2 - Polyarylene sulfide resin composition, molded article, composite molded article, and methods for producing the same - Google Patents

Description

The present invention relates to a polyarylene sulfide resin composition, a molded article, a composite molded body, and a method for producing the same.

Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resins, such as polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin, are known to have a high melting point and excellent heat resistance, as well as excellent mechanical strength, chemical resistance, moldability, and dimensional stability. Therefore, PAS resins are generally mixed with additives such as fillers and elastomers, and melt-kneaded so that these are dispersed in a matrix made of PAS resin to form a PAS resin composition, which is then melt-molded and processed into molded products to be used as electrical and electronic equipment parts, automobile parts, etc.

These parts are often bonded to part materials made of epoxy resins and the like as a secondary process. However, PAS resin has relatively poor adhesion to other resins, especially to epoxy resins. For this reason, for example, when joining PAS resins together with epoxy adhesives, joining PAS resins to other materials, or sealing electrical and electronic parts with epoxy resins, the poor adhesion between PAS resins and curable resin compositions containing epoxy resins (hereinafter sometimes referred to as epoxy resin adhesion) has been a problem.

In order to improve the deterioration of epoxy resin adhesion, a method has been proposed for improving the epoxy resin adhesion and cold and thermal shock resistance of molded products in a well-balanced manner by using a PAS resin composition containing a specific amount of PAS resin, a novolac type epoxy resin, a bisphenol type epoxy resin, glass fibers, and glass flakes (see Patent Document 1). However, even in this case, the epoxy resin adhesion of the PAS resin molded product is low, and further improvement of the epoxy resin adhesion was desired. In addition, the PAS resin composition and the PAS resin molded product are heated to a temperature above the melting point of the PAS resin during production to make it in a molten state, but there is a tendency for the amount of gas generated at that time (hereinafter sometimes referred to as the amount of gas generated during melting) to be large. This can lead to a deterioration of the working environment due to odor problems and a decrease in maintainability due to mold contamination, and further, stains and tar-like substances can adhere to the mold surface and molded product surface, so the development of a PAS resin composition with a low amount of gas generated during melting was desired.

Therefore, a PAS resin composition containing a specific amount of a naphthyl ether type epoxy resin, a molded article, and a composite molded article of an epoxy resin molded article have been proposed (see Patent Document 2). However, the effect of improving the epoxy resin adhesiveness and the effect of reducing the amount of gas generated during melting are not sufficient, and there is a demand for further improvement of the epoxy resin adhesiveness and further reduction of the amount of gas generated during melting.

International Publication No. 2013/141363 JP 2018-104534 A

The problems that the present invention aims to solve are to provide a PAS resin composition that generates a low amount of gas when melted and that produces a molded article with excellent epoxy resin adhesion, to provide a molded article with excellent epoxy resin adhesion obtained by molding the composition, to provide a composite molded article in which the molded article is bonded to a cured product of a curable resin composition containing an epoxy resin, and to provide a method for producing the composite molded article, to provide a method for producing a PAS resin composition that produces a molded article with excellent epoxy resin adhesion while suppressing the amount of gas generation, and to provide a method for producing a molded article with excellent epoxy resin adhesion while suppressing the amount of gas generation.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that blending an epoxy resin having an alicyclic structure with a PAS resin as an essential component provides excellent thermal decomposition resistance, reduces the amount of gas generated during melting, and exhibits excellent epoxy resin adhesion due to the epoxy groups, which led to the completion of the present invention.

That is, the present invention provides a composition comprising a polyarylene sulfide resin (A) and an epoxy resin (B) having an alicyclic structure (α) and an aromatic structure (β) in a repeating unit as essential components,
The polyarylene sulfide resin composition is characterized in that the epoxy resin (B) is in the range of 0.01 to 50 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A).

In addition, the present invention relates to a molded article obtained by molding the PAS resin composition.

The present invention further relates to a composite molded article formed by bonding a molded article made by molding the PAS resin composition to a cured product of a curable resin composition containing an epoxy resin.

The present invention also relates to a method for producing a polyarylene sulfide resin composition, which is characterized by blending polyarylene sulfide resin (A) and epoxy resin (B) having an alicyclic structure (α) as essential components, and melt-kneading the mixture at a temperature equal to or higher than the melting point of polyarylene sulfide resin (A).

In addition, the present invention relates to a method for producing a molded article by melt molding the PAS resin composition.

The present invention further relates to a method for producing a composite molded product, which includes a step of bonding a molded product obtained by molding the PAS resin composition to a cured product of a curable resin composition containing an epoxy resin.

According to the present invention, it is possible to provide a PAS resin composition that generates a low amount of gas when melted and that produces a molded article with excellent epoxy resin adhesion, to provide a molded article with excellent epoxy resin adhesion obtained by molding the PAS resin composition, to provide a composite molded article in which the molded article is bonded to a cured product of a curable resin composition containing an epoxy resin, and to provide a method for producing the composite molded article, to provide a method for producing a PAS resin composition that produces a molded article with excellent epoxy resin adhesion while suppressing the amount of gas generation, and to provide a method for producing a molded article with excellent epoxy resin adhesion while suppressing the amount of gas generation.

The PAS resin composition of the present invention comprises, as essential components, a polyarylene sulfide resin (A) and an epoxy resin (B) having an alicyclic structure (α) and an aromatic structure (β) in a repeating unit;
The epoxy resin (B) is contained in an amount of 0.01 to 50 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A).

The PAS resin composition of the present invention is composed of PAS resin (A) as an essential component. The PAS resin used in the present invention has a resin structure in which a repeating unit is a structure in which an aromatic ring and a sulfur atom are bonded, and specifically, the PAS resin has the following general formula (1):

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

(wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group), and, if necessary, a structural portion represented by the following general formula (2):

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

The trifunctional structural unit represented by formula (2) is preferably in the range of 0.001 to 3 mol %, particularly preferably 0.01 to 1 mol %, based on the total number of moles of the trifunctional structural unit and other structural units.

Here, the structural portion represented by the general formula (1), particularly ^R1 and ^R2 in the formula, are preferably hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin. In this case, examples of the structural portion include those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4).

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

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

The PAS resin may contain not only the structural moieties represented by the general formulas (1) and (2) but also the structural moieties represented by the following structural formulas (5) to (8):

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

The structural moiety represented by the general formula (1) and the structural moiety represented by the general formula (2) may be contained in an amount of 30 mol % or less of the total of the structural moieties represented by the general formula (1) and the general formula (2). In particular, in the present invention, it is preferable that the structural moieties represented by the general formulas (5) to (8) are 10 mol % or less in terms of the heat resistance and mechanical strength of the PAS resin. When the structural moieties represented by the general formulas (5) to (8) are contained in the PAS resin, the bonding mode thereof may be either a random copolymer or a block copolymer.

The PAS resin may also have naphthyl sulfide bonds in its molecular structure, but this is preferably 3 mol % or less, and more preferably 1 mol % or less, relative to the total number of moles including other structural parts.

The physical properties of the PAS resin are not particularly limited as long as they do not impair the effects of the present invention, but are as follows:

(Melt Viscosity)
The melt viscosity of the PAS resin used in the present invention is not particularly limited, but the melt viscosity (V6) measured at 300°C is preferably in the range of 2 to 1000 [Pa·s], more preferably in the range of 10 to 500 [Pa·s], and particularly preferably in the range of 60 to 200 [Pa·s], since this provides a good balance between fluidity and mechanical strength. However, in the present invention, the melt viscosity (V6) is a value measured by holding the PAS resin at 300°C, a load of 1.96×10 ⁶ Pa, L/D=10 (mm)/1 (mm) for 6 minutes using a Shimadzu flow tester, CFT-500D.

(Non-Newtonian Exponents)
The non-Newtonian index of the PAS resin (A) used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.90 or more to 2.00 or less. When a linear type PAS resin is used, the non-Newtonian index is preferably 0.90 or more, more preferably 0.95 or more, and preferably 1.50 or less, more preferably 1.20 or less. Such a PAS resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is a value calculated using the following formula by measuring the shear rate and shear stress using a capillograph under the conditions of 300 ° C. and the ratio of the orifice length (L) to the orifice diameter (D), L / D = 40.

［ただし、ＳＲは剪断速度（秒^－１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］Ｎ値は１に近いほどＰＰＳは線状に近い構造であり、Ｎ値が高いほど分岐が進んだ構造であることを示す。

[where SR is shear rate (sec ^-1 ), SS is shear stress (dynes/ ^cm2 ), and K is a constant.] The closer the N value is to 1, the more linear the PPS structure is, and the higher the N value, the more branched the structure is.

(Production method)
The method for producing the PAS resin (A) is not particularly limited, but examples thereof include 1) a method in which a dihalogenoaromatic compound is added in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added, and polymerized; 2) a method in which a dihalogenoaromatic compound is added in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added, and polymerized; and 3) a method in which p-chlorothiophenol is added, and if necessary, other copolymerization components are added, and self-condensed. Among these methods, method 2) is generally used and is preferred. During the reaction, an alkali metal salt of a carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above-mentioned 2) methods, there is a method for producing a PAS resin by introducing a water-containing sulfidizing agent into a mixture containing a heated organic polar solvent and a dihalogeno-aromatic compound at a rate at which water can be removed from the reaction mixture, and then reacting the dihalogeno-aromatic compound and the sulfidizing agent in the organic polar solvent, and optionally adding a polyhalogeno-aromatic compound, and controlling the amount of water in the reaction system to within a range of 0.02 to 0.5 moles per mole of the organic polar solvent (see JP-A-07-228699). Particularly preferred is a method in which a dihalogeno-aromatic compound and, if necessary, a polyhalogeno-aromatic compound or other copolymerization component are added in the presence of a metal sulfide and an aprotic polar organic solvent, and an alkali metal hydrosulfide and an organic acid alkali metal salt are reacted while controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 mol per mol of the sulfur source and the amount of water in the reaction system to be 0.02 mol or less per mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet). Specific examples of the dihalogeno aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-di Examples of the polyhalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. The halogen atoms contained in the above compounds are preferably chlorine atoms or bromine atoms.

The method for post-treating the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited, but may be, for example, (1) after the polymerization reaction is completed, the reaction mixture is left as is or after the addition of an acid or base, and the solvent is removed under reduced pressure or normal pressure, and the solid matter remaining after the solvent removal is washed once or twice or more times with a solvent such as water, the reaction solvent (or an organic solvent having a similar solubility to the low molecular weight polymer), acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, filtered, and dried; or (2) after the polymerization reaction is completed, the reaction mixture is washed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, or aliphatic hydrocarbons (a solvent that is soluble in the polymerization solvent used and has poor solubility at least for PAS). (3) After the polymerization reaction is completed, the reaction mixture is added with a reaction solvent (or an organic solvent having a solubility equivalent to that of the low molecular weight polymer) and stirred, and then filtered to remove the low molecular weight polymer. The mixture is then washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, filtered, and dried. (4) After the polymerization reaction is completed, water is added to the reaction mixture, washed with water, filtered, and if necessary, acid is added during the water washing for acid treatment, and the mixture is dried. (5) After the polymerization reaction is completed, the reaction mixture is filtered, and if necessary, washed with the reaction solvent once or twice, filtered, and dried.

In the post-treatment methods exemplified above in (1) to (5), the PAS resin may be dried in a vacuum, in air, or in an inert gas atmosphere such as nitrogen.

The PAS resin composition of the present invention contains, as an essential component, an epoxy resin (B) having an alicyclic structure (α) and an aromatic ring structure (β) as repeating units.
The epoxy resin (B) is not particularly limited in its specific structure or manufacturing method, etc., so long as it has an alicyclic structure (α) and an aromatic ring structure (β) in the molecule, and various kinds of epoxy resins can be used. An example of the epoxy resin (B) having an alicyclic structure (α) and an aromatic ring structure (β) in the molecule is polyglycidyl ether of an addition polymer of an unsaturated alicyclic compound (α1) and a phenolic hydroxyl group-containing aromatic compound (β1).

The unsaturated alicyclic compound (α1) is not particularly limited as long as it has an alicyclic structure in its molecular structure and can react with the phenolic hydroxyl group-containing aromatic compound (β1) to produce an addition polymer, but examples of such compounds include those having an alicyclic structure in its molecular structure and having two or more unsaturated bonds (carbon-carbon double bonds). Specific examples include alicyclic conjugated diene compounds such as cyclopentadiene and methylcyclopentadiene, and Diels-Alder reaction products of at least one compound selected from the group consisting of the alicyclic conjugated diene compounds and linear conjugated diene compounds such as butadiene, isoprene, and piperylene. Among these, dicyclopentadiene is preferred because of its excellent epoxy adhesiveness and the ability to further reduce the amount of gas generated during melting.

The phenolic hydroxyl group-containing aromatic compound (β1) may be, for example, phenol, cresol, naphthol, anthracenol, or a compound in which one or more hydrogen atoms on the aromatic ring of these compounds are substituted with an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, a halogen atom, or the like. Of these, phenol and cresol are preferred because they have excellent epoxy adhesive properties and can further reduce the amount of gas generated when melted.

The addition polymerization reaction between the unsaturated alicyclic compound (α1) and the phenolic hydroxyl group-containing aromatic compound (β1) can be carried out by a known, commonly used method. One example of such a method is a method in which the reaction is carried out under acid catalyst conditions at a temperature of about 70 to 90°C. The reaction ratio of the two is appropriately adjusted, but it is preferable that the molar ratio of the two [(α1)/(β1)] is in the range of 1/1.5 to 1/5 in order to obtain a molecular weight with excellent heat resistance.

The polyglycidyl etherification reaction of the reaction product obtained by the addition polymerization reaction of the unsaturated alicyclic compound (α1) and the phenolic hydroxyl group-containing aromatic compound (β1) (hereinafter, the reaction product obtained by the addition polymerization reaction may be simply referred to as the "addition reaction product") can be carried out by a known, conventional method. One example of such a method is to use 2 to 10 moles of epihalohydrin per mole of phenolic hydroxyl group in the addition polymerization product, and react for 0.5 to 10 hours at a temperature of 20 to 120°C while adding 0.9 to 2.0 moles of a basic catalyst per mole of phenolic hydroxyl group all at once or in portions.

The epoxy equivalent of the epoxy resin (B) is not particularly limited, but is preferably 100 g/equivalent or more, more preferably 200 g/equivalent or more, and even more preferably 270 g/equivalent or more, and preferably 500 g/equivalent or less, more preferably 400 g/equivalent or less, and even more preferably 300 g/equivalent or less, in terms of excellent epoxy adhesion and further reducing the amount of gas generated during melting. The epoxy equivalent is a value measured by a method conforming to JIS K 7236.

The softening point of the epoxy resin (B) is not particularly limited, but is preferably in the range of 50°C or higher, more preferably 65°C or higher, and even more preferably 75°C or higher, and preferably 150°C or lower, more preferably 130°C or lower, and even more preferably 110°C or lower, in order to provide excellent epoxy adhesiveness and further reduce the amount of gas generated during melting. The softening point is measured according to a method in accordance with JIS K7234.

In the present invention, a commercially available epoxy resin may be used as the epoxy resin (B). Specific examples include "EPICLON HP-7200L", "EPICLON HP-7200", "EPICLON HP-7200H", "EPICLON HP-7200HH", and "EPICLON HP-7200HHH" manufactured by DIC Corporation, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "EP-4085" and "EP-4088S" manufactured by ADEKA Corporation, and "ZX-1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

The specific structure of the epoxy resin (B) is, for example, the following general formula:

で表される高分子化合物を含む樹脂などが挙げられる。式中、ｎは繰り返し単位を表し、０以上から、好ましくは１０以下、より好ましく５以下の範囲である。

In the formula, n represents a repeating unit and is in the range of 0 or more, preferably 10 or less, and more preferably 5 or less.

The proportion of the epoxy resin (B) in the PAS resin composition is in the range of 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 50 parts by mass or less, preferably 35 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). Within the above range, the PAS resin molded product has excellent epoxy resin adhesion and mechanical strength, and also has excellent flowability by reducing the amount of gas generated when the PAS resin composition is melted and suppressing thickening during melt molding.

The PAS resin composition of the present invention may contain a filler as an optional component, if necessary. As these fillers, known and commonly used materials may be used as long as they do not impair the effects of the present invention. For example, fillers of various shapes, such as fibrous ones and non-fibrous ones such as granular and plate-shaped ones, may be used. Specifically, fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers may be used. In addition, non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber, and calcium sulfate may also be used.

In the present invention, the filler is not an essential component, and when it is blended, its content is not particularly limited as long as it does not impair the effects of the present invention. The blending amount of the filler is, for example, preferably 1 part by mass or more, more preferably 10 parts by mass or more, and preferably 600 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of the PAS resin (A). In such a range, the resin composition exhibits good mechanical strength and moldability, which is preferable.

The PAS resin composition of the present invention can be blended with a silane coupling agent as an optional component, if necessary. The silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but preferred examples include silane coupling agents having a functional group that reacts with a carboxy group, such as an epoxy group, an isocyanato group, an amino group, or a hydroxyl group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. In the present invention, a silane coupling agent is not an essential component, but when it is used, the amount of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, and is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). In such a range, the resin composition has good corona resistance and moldability, especially releasability, and the molded product exhibits excellent adhesion to the epoxy resin while also improving mechanical strength, which is preferable.

The PAS resin composition of the present invention may contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers, among which polyolefin-based elastomers are preferred. When these elastomers are added, the amount of the elastomers is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, to preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of PAS resin (A). In such a range, the impact resistance of the resulting PAS resin composition is improved, which is preferable.

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

The above-mentioned thermoplastic elastomers may be used alone or in combination of two or more.

In addition to the above components, the PAS resin composition of the present invention may further contain synthetic resins such as polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenolic resin, urethane resin, and liquid crystal polymer (hereinafter simply referred to as synthetic resin) as optional components depending on the application. The synthetic resin is not an essential component in the present invention, but when it is added, the ratio of the synthetic resin is not particularly limited as long as it does not impair the effects of the present invention, and it differs depending on each purpose and cannot be generally defined, but the ratio of the synthetic resin to be added in the resin composition of the present invention is, for example, in the range of about 5 to 15 parts by mass per 100 parts by mass of PAS resin (A). In other words, the ratio of PAS resin (A) to the total of PAS resin (A) and synthetic resin is preferably in the range of (100/115) or more, more preferably in the range of (100/105) or more, based on mass.

The PAS resin composition of the present invention may also contain other known and commonly used additives as optional components, such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, and coupling agents, as necessary. These additives are not essential components, and may be used, for example, in an amount of preferably 0.01 to 1000 parts by mass per 100 parts by mass of PAS resin (A), adjusted appropriately according to the purpose and application so as not to impair the effects of the present invention.

The method for producing the PAS resin composition of the present invention involves melt-kneading the PAS resin (A) and the epoxy resin (B) as essential components at a temperature equal to or higher than the melting point of the PAS resin (A).

The preferred method for producing the PAS resin composition of the present invention is to dry blend the PAS resin (A) and the essential components of the epoxy resin (B), and, if necessary, optional components such as fillers, in various forms such as powder, pellets, and fine pieces in a ribbon blender, Henschel mixer, V blender, etc., so that the content is as described above, and then to feed them into a known melt kneader such as a Banbury mixer, mixing roll, single-screw or twin-screw extruder, and kneader, and melt kneading them in a temperature range in which the resin temperature is equal to or higher than the melting point of the PAS resin, preferably in a temperature range of melting point + 10°C or higher, more preferably in a temperature range of melting point + 10°C to melting point + 100°C, and even more preferably in a temperature range of melting point + 20°C to melting point + 50°C. The components may be added and mixed into the melt kneader simultaneously or in portions.

As the melt kneader, a twin-screw kneading extruder is preferred from the viewpoint of dispersibility and productivity. For example, it is preferred to melt knead while appropriately adjusting the resin component discharge rate in the range of 5 to 500 (kg/hr) and the screw rotation speed in the range of 50 to 500 (rpm), and it is even more preferred to melt knead under conditions where the ratio (discharge rate/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). In addition, when adding fillers or additives among the components, it is preferred from the viewpoint of dispersibility to feed them into the twin-screw kneading extruder from a side feeder. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin input section to the side feeder to the total screw length of the twin-screw kneading extruder is in the range of 0.1 to 0.9. Of these, it is particularly preferred that the ratio is in the range of 0.3 to 0.7.

The PAS resin composition of the present invention obtained by melt kneading in this manner is a molten mixture containing the essential component PAS resin (A), the epoxy resin (B), and optional components added as necessary and components derived therefrom. After the melt kneading, it is preferably processed into pellets, chips, granules, powder, etc., by a known method, and then pre-dried at a temperature of 100 to 150°C as necessary, before being used for various molding processes.

The PAS resin composition of the present invention produced by the above-mentioned production method has a morphology in which the essential component epoxy resin (B), components derived therefrom, and optional components added as necessary are dispersed in the matrix of PAS resin. As a result, the PAS resin molded product has excellent epoxy resin adhesion, mechanical strength, and flame retardancy, and also has excellent fluidity by reducing the amount of gas generated when the PAS resin composition is melted and by suppressing thickening during melt molding.

The PAS resin composition of the present invention can be subjected to various molding processes such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding applications due to its excellent releasability. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a normal general method. For example, in an injection molding machine, the PAS resin composition is melted at a resin temperature in a temperature range of the melting point of the PAS resin or higher, preferably in a temperature range of the melting point + 10°C or higher, more preferably in a temperature range of the melting point + 10°C to the melting point + 100°C, and even more preferably in a temperature range of the melting point + 20 to the melting point + 50°C, and then the resin is injected into a mold from a resin outlet and molded. At that time, the mold temperature may also be set to a known temperature range, for example, room temperature (23°C) to 300°C, preferably 120 to 180°C.

Molded articles made from the PAS resin composition of the present invention not only have excellent adhesion to epoxy resins, but also have excellent mechanical strength, particularly the bending strength of the resin in the TD direction during injection molding.

The PAS resin molded article of the present invention has excellent adhesion to a curable resin composition containing an epoxy resin. The curable resin composition containing an epoxy resin is preferably a composition obtained by mixing an epoxy resin with a curing agent.

The epoxy resin used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include bisphenol-type epoxy resins, novolac-type epoxy resins, naphthyl ether-type epoxy resins, and the epoxy resin (B), among which bisphenol-type epoxy resins are preferred due to their excellent adhesive properties.

The type of epoxy resin in the bisphenol type epoxy resin includes glycidyl ethers of bisphenols, specifically bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin.

In addition, the novolac type epoxy resin may be obtained by reacting a novolac type phenolic resin obtained by a condensation reaction between a phenol and an aldehyde with an epihalohydrin. Specific examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, and brominated phenol novolac type epoxy resin.

These epoxy resins are preferably used by undergoing a curing reaction with a curing agent.

In the present invention, the curing agent for curing the epoxy resin is not particularly limited as long as it is generally used as a curing agent for epoxy resins, but examples thereof include amine-type curing agents, phenolic resin-type curing agents, acid anhydride-type curing agents, latent curing agents, etc.

As the amine-type curing agent, known ones can be used, such as aliphatic polyamines, aromatic polyamines, heterocyclic polyamines, and the like, as well as their epoxy adducts, Mannich modified products, and modified products of polyamides. Specific examples include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, and the like. Of these, m-xylenediamine and 1,3-bisaminomethylcyclohexane are particularly preferred because of their excellent curing properties.

Phenol resin-type hardeners that can be used include known hardeners, such as bisphenols such as bisphenol A, bisphenol F, and biphenol, trifunctional phenolic compounds such as tri(hydroxyphenyl)methane and 1,1,1-tri(hydroxyphenyl)ethane, phenol novolac, and cresol novolac.

As the acid anhydride type curing agent, known ones can be used, such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

Examples of latent hardeners include dicyandiamide, imidazole, BF3-amine complexes, and guanidine derivatives.

These curing agents can be used alone or in combination of two or more. In addition, it is also possible to use them in combination with a curing accelerator as appropriate, as long as the effects of the present invention are not impaired. Various types of curing accelerators can be used, including, for example, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.

The curable resin composition containing the epoxy resin used in the present invention may undergo a curing reaction without a solvent, but may also undergo a curing reaction in a solvent such as benzene, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile, chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyrrolidone, isopropyl alcohol, isobutanol, or t-butyl alcohol.

In the curable resin composition used in the present invention, the ratio of the epoxy resin to the curing agent is not particularly limited as long as it is a known ratio within a range that does not impair the effects of the present invention, but since it provides a cured product with excellent curing properties and excellent heat resistance and chemical resistance, it is preferable to use an amount in which the active groups in the curing agent are 0.7 to 1.5 equivalents per total equivalent of epoxy groups in the epoxy resin component.

The molded article obtained by molding the PAS resin composition of the present invention has excellent adhesion to epoxy resins, and can therefore be suitably used as a composite molded article in which a PAS resin and a cured product of a curable resin composition containing an epoxy resin are bonded together.
The manufacturing method may be any known method as long as it does not impair the effects of the present invention, but may include a method in which a molded article obtained by molding a PAS resin composition is contacted with a curable resin composition containing an epoxy resin and the curable resin composition is cured.

Major applications of the composite moldings include housings for various home appliances, mobile phones, and electronic devices such as PCs (Personal Computers), protective and supporting materials for box-shaped integrated modules of electric and electronic components, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other representative electric and electronic parts; VTR parts, television parts, irons, hair dryers, Home and office electrical appliance parts such as rice cooker parts, microwave oven parts, audio parts, audio/visual equipment parts such as audio/laser discs, compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and water-related equipment parts such as water heaters, bath water volume and temperature sensors; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, and other machine related parts; optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, and watches; alternator terminals, alternator connectors, brush holders slip rings, IC regulators, potentiometer bases for light dimmers, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel, exhaust systems and intake systems, air intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, hot air flow control valves for heating, brushless hoses for radiator motors It can also be used for automobile and vehicle related parts such as rotors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and a variety of other applications.

The present invention will be described in more detail below with reference to specific examples. The analysis of the resins produced in the production examples was carried out under the following conditions.

Measurement Example 1 Measurement of Melt Viscosity of Polyphenylene Sulfide Resin The polyphenylene sulfide resin produced in the Reference Example was measured using a Shimadzu Corporation flow tester, CFT-500D, at 300°C, load: 1.96 x ¹⁰⁶ Pa, L/D = 10 (mm)/1 (mm) after holding for 6 minutes.

(Production Example 1) Production of polyphenylene sulfide resin (A-1) 33.222 kg (226 moles) of p-dichlorobenzene (hereinafter abbreviated as "p-DCB"), 2.280 kg (23 moles) of NMP, 27.300 kg of 47.23 mass% NaSH aqueous solution (230 moles as NaSH), and 18.533 g of 49.21 mass% NaOH aqueous solution (228 moles as NaOH) were charged into a 150-liter autoclave equipped with an agitator connected to a pressure gauge, a thermometer, a condenser, a decanter, and a rectification column, and the mixture was heated to 173°C over 5 hours under a nitrogen atmosphere while stirring, and 27.300 kg of water was distilled off, after which the autoclave was sealed. The p-DCB distilled by azeotropy during dehydration was separated in a decanter and returned to the autoclave as needed. After completion of dehydration, the autoclave was in a state in which the fine particle-like anhydrous sodium sulfide composition was dispersed in the p-DCB. The NMP content in this composition was 0.069 kg (0.7 mol), which indicated that 97 mol% (22.3 mol) of the charged NMP was hydrolyzed to a ring-opened form of NMP (4-(methylamino)butyric acid) sodium salt (hereinafter abbreviated as "SMAB"). The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atom present in the autoclave. Since the theoretical amount of dehydration when the charged NaSH and NaOH are all converted to anhydrous Na ₂ S is 27.921 g, it was shown that, of the remaining water amount of 621 g (34.5 mol) in the autoclave, 401 g (22.3 mol) was consumed in the hydrolysis reaction of NMP and NaOH and was not present in the autoclave as water, and the remaining 220 g (12.2 mol) remained in the autoclave in the form of water or crystal water. The amount of water in the autoclave was 0.053 mol per mol of sulfur atom present in the autoclave.

After the above dehydration process was completed, the inside temperature was cooled to 160°C, a solution containing 47.492 kg (479 moles) of NMP was charged, and the temperature was raised to 185°C. The amount of water in the autoclave was 0.025 moles per mole of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the distillation tower was opened, and the inside temperature was raised to 200°C over one hour. At this time, cooling and valve opening were controlled so that the outlet temperature of the distillation tower was 110°C or less. The mixed vapor of p-DCB and water distilled was condensed in a condenser and separated in a decanter, and p-DCB was returned to the autoclave. The amount of distilled water was 179 g (9.9 moles), and the amount of water in the autoclave was 41 g (2.3 moles), which was 0.005 moles per mole of NMP charged after dehydration and 0.010 moles per mole of sulfur atoms present in the autoclave. The amount of SMAB in the autoclave was the same as during dehydration, 0.097 moles per mole of sulfur atom present in the autoclave.

Then, the internal temperature was raised from 200°C to 230°C over 3 hours, stirred at 230°C for 1 hour, and then heated to 250°C and stirred for 1 hour. The gauge pressure at the internal temperature of 200°C was 0.03 MPa, and the final gauge pressure was 0.30 MPa. After cooling, 6.5 kg of the obtained slurry was poured into 30 liters of 80°C hot water and stirred for 1 hour, then filtered. The cake was stirred again with 30 liters of hot water for 1 hour, washed, and then filtered. Next, 30 liters of water was added to the obtained cake, the pH was adjusted to 4.5 with acetic acid, stirred at room temperature for 1 hour, and then filtered. The operation of adding 30 liters of hot water to the obtained cake, stirring for 1 hour, and filtering was repeated twice, and the mixture was dried overnight at 120°C using a hot air circulation dryer to obtain a carboxyl group-containing PPS resin (hereinafter, A-1) in the form of white powder. The melt viscosity of the obtained polymer was 98 Pa·s.

(Examples 1 and 2 and Comparative Examples 1 to 4) Production of PPS resin composition According to the composition components and compounding amounts (all parts by mass) shown in Tables 1 and 2, each material was uniformly mixed in a tumbler. Thereafter, the compounded materials were charged into a vented twin-screw extruder "TEM-35B" manufactured by Toshiba Machine Co., Ltd., and melt-kneaded at a resin component discharge rate of 25 kg/hr, a screw rotation speed of 250 rpm, a ratio of the resin component discharge rate (kg/hr) to the screw rotation speed (rpm) (discharge rate/screw rotation speed) = 0.1 (kg/hr rpm), and a set resin temperature of 330°C to obtain pellets of the resin composition. The following various evaluation tests were carried out using these pellets. The test and evaluation results are shown in Tables 1 and 2.

(Measurement Example 3) Observation of adhesive strength between PPS resin molded product and epoxy resin and state of adhesive surface
The obtained pellets were fed to an injection molding machine (SG75-HIPRO-MIII) manufactured by Sumitomo-Nestal Co., Ltd., with a cylinder temperature set at 320°C, and injection molding was performed using a mold for molding ASTM No. 1 dumbbell pieces, with the mold temperature adjusted to 130°C, to obtain ASTM No. 1 dumbbell pieces. The obtained ASTM No. 1 dumbbell pieces were divided into two equal parts from the center, and a spacer (thickness: 1.8 to ^2.2 mm, opening: 13 mm x 25 mm) prepared so that the contact area with the curable resin composition containing epoxy resin was 50 mm2 was sandwiched between the two ASTM No. 1 dumbbell pieces, and fixed using a clip. Then, a curable resin composition containing epoxy resin (two-liquid epoxy resin manufactured by Nagase ChemteX Corporation, base agent: XNR5002, curing agent: XNH5002, blending ratio of base agent: curing agent = 100: 90) was injected into the opening, and the mixture was heated in a hot air dryer set at 135°C for 3 hours to cure and adhere. After cooling for one day at 23°C, the spacer was removed, and the resulting test piece was used to measure the tensile breaking strength at 23°C with a tensile speed of 5 mm/sec, a support distance of 80 mm, and a Shimadzu tensile tester "AG-X Series." The value obtained by dividing the strength by the adhesive area was taken as the epoxy adhesive strength. In addition, the condition of the bonded surfaces was observed at the time of fracture. Note that "cohesive failure" means that the adhesive layer itself is broken, "base material failure" means that the substrate (here, the above-mentioned ASTM No. 1 dumbbell specimen) is broken, and "interface peeling" means that the adhesive layer and substrate are peeled off at the interface.

(Measurement Example 4) Weight Loss (Amount of Gas Generated) of PPS Resin Composition Upon Melting
The pellets of the PPS resin composition obtained in Examples 1 and 2 and Comparative Examples 1 to 5 were dried at 150°C for 1 hour under nitrogen flow. Next, 10 g of the pellets were weighed out and heated at 325°C for 1 hour, and the weight loss rate before and after heating was measured. This weight loss rate corresponds to the amount of gas generated from the pellets during heating. The smaller the weight loss rate (amount of gas generated), the better from the standpoints of mold maintainability, surface appearance, mechanical properties, and moldability.

In Tables 1 and 2, the blending ratios of the blended resins and materials are expressed in parts by mass, and the following were used.
Epoxy resin B-1: "EPICLON HP-7200H" manufactured by DIC Corporation (epoxy group equivalent: 274 g/equivalent, softening point: 83°C)
B-2: "EPICLON HP-7200HHH" (epoxy group equivalent: 285 g/equivalent, softening point: 103°C)
b-3: Bisphenol A type epoxy resin "EPICLON (registered trademark) 1050" manufactured by DIC Corporation (epoxy equivalent weight 450 g/equivalent)
b-4: Cresol novolac epoxy resin "EPICLON (registered trademark) N680" (epoxy equivalent: 210 g/equivalent) manufactured by DIC Corporation
Glass fiber b-5: The naphthyl ether type epoxy resin used was produced by the following production method.

(Production Example 2) Production of epoxy resin (b-5) 160 parts by mass of 2,7-dihydroxynaphthalene, 25 parts by mass of benzyl alcohol, 160 parts by mass of xylene, and 2 parts by mass of paratoluenesulfonic acid monohydrate were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, and stirred at room temperature while blowing in nitrogen. The temperature was raised to 140°C, the water produced was distilled out of the system, and the xylene distilled together with the water was returned to the reaction system while stirring for 4 hours. The temperature was then raised to 150°C, and the water and xylene produced were distilled out of the system while stirring for 3 hours. After the reaction was completed, 2 parts by mass of a 20% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was dried under reduced pressure to obtain 178 parts by mass of a polyarylene ether resin intermediate (b-5-1). The hydroxyl equivalent of the intermediate (b-5-1) was 169 g/equivalent, and the softening point was 130°C.

The polyarylene ether resin intermediate (b-5-1) was subjected to FD-MS (double focusing mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.) and FD-MS of a trimethylsilylated product of the polyarylene ether resin intermediate (b-5-1) were measured, and the production of the following compound was confirmed.
1. 2,7-dihydroxynaphthalene with one benzyl group added (M ⁺ = 250)
2. 2,7-dihydroxynaphthalene with two benzyl groups (M ⁺ = 340)
3. A compound represented by the following structural formula (a) in which n is 1 (M ⁺ =446)
4. A compound represented by the following structural formula (a) in which n is 2 (M ⁺ =588)
5. A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 1 in the following structural formula (a) (M ⁺ =660).
6. A compound represented by the following structural formula (a) in which n is 3 (M ⁺ =730)
7. A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 2 in the following structural formula (a) (M ⁺ = 802).
8. A compound represented by the following structural formula (a) in which n is 4 (M ⁺ =873)
9. A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 3 in the following structural formula (a) (M ⁺ = 944)
10. A compound in which two trimethylsilyloxynaphthyl groups are added to a compound in which n is 2 in the following structural formula (a) (M ⁺ =1016).
11. Compounds in which one or two benzyl groups have been added to any of the compounds 3 to 10 above

（式中ｎは０又は１以上の整数、ＴＭＳはトリメチルシリル基である。）

(In the formula, n is an integer of 0 or 1 or more, and TMS is a trimethylsilyl group.)

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 169 parts by mass of the polyarylene ether resin intermediate (b-5-1) obtained above, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and 2 parts by mass of tetraethylbenzylammonium chloride were charged and dissolved while purging with nitrogen gas. After heating to 65°C, the pressure was reduced to the pressure at which azeotropy occurred, and 90 parts by mass of 49% aqueous sodium hydroxide solution was dropped over 5 hours. Stirring was then continued for 0.5 hours under the same conditions. During this time, the distillate that had been distilled by azeotropy was separated using a Dean-Stark trap, the aqueous layer was removed, and the organic layer was returned to the reaction system while the reaction was carried out. After that, unreacted epichlorohydrin was distilled off by reduced pressure distillation. 432 parts by mass of methyl isobutyl ketone and 130 parts by mass of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 10 parts by mass of a 10% aqueous sodium hydroxide solution was added and reacted at 80°C for 2 hours. Then, the mixture was washed with 150 parts by mass of water until the pH of the washing water became neutral. The system was dehydrated by azeotropy, and after passing through precision filtration, it was dried under reduced pressure conditions to obtain 230 parts by mass of epoxy resin (b-5). The softening point of epoxy resin (b-5) was 100°C, and the epoxy equivalent was 277 g/equivalent.

C-1: Chopped strand (E-glass, average fiber length 200 μm, average diameter 10 μm, surface treated with epoxy binder)

Claims (12)

a polyarylene sulfide resin (A) and an epoxy resin (B) having an alicyclic structure (α) and an aromatic structure (β) in a repeating unit thereof as essential components;
The epoxy resin (B) is in the range of 0.01 to 50 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A);
The epoxy resin (B) is represented by the following general formula (1):

(wherein n is in the range of 0 to 10) and has a softening point in the range of 83 to 150°C. The resin composition according to claim 1, wherein the epoxy equivalent of the epoxy resin (B) is in the range of 100 to 500 g/equivalent. The resin composition according to claim 1 or 2, wherein the non-Newtonian index of the polyarylene sulfide resin (A) is in the range of 0.90 or more and 2.00 or less. The polyarylene sulfide resin composition according to any one of claims 1 to 3, which is a melt-kneaded product. A molded article obtained by molding the polyarylene sulfide resin composition according to any one of claims 1 to 4. A composite molded product formed by bonding the molded product according to claim 5 to a cured product of a curable resin composition containing an epoxy resin. blending a polyarylene sulfide resin (A) and an epoxy resin (B) having an alicyclic structure (α) as essential components, and melt-kneading the mixture at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A);
The epoxy resin (B) is in the range of 0.01 to 50 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A);
The epoxy resin (B) is represented by the following general formula (1):

(wherein n is in the range of 0 to 10) and having a softening point in the range of 83 to 150°C. The method for producing a resin composition according to claim 7, wherein the epoxy equivalent of the epoxy resin (B) is in the range of 100 to 500 g/equivalent. The method for producing a resin composition according to claim 7 or 8, wherein the non-Newtonian index of the polyarylene sulfide resin (A) is in the range of 0.90 or more and 2.00 or less. A method for producing a molded product, comprising a step of melt molding a polyarylene sulfide resin composition produced by the method according to any one of claims 7 to 9. A method for producing a composite molded product, comprising contacting the molded product according to claim 5 with a curable resin composition containing an epoxy resin, and then curing the curable resin composition. A method for producing a composite molded product, comprising contacting a molded product produced by the method according to claim 10 with a curable resin composition containing an epoxy resin, and then curing the curable resin composition.