JP6180075B2 - Polyarylene sulfide resin composition - Google Patents

Description

  The present invention relates to a composition based on polyphenylene sulfide and a molded article thereof. More particularly, the present invention relates to a polyarylene sulfide resin composition having improved electrical properties, particularly excellent insulation life, containing polyphenylene sulfide, and a molded article thereof.

  Polyarylene sulfide (hereinafter abbreviated as “PAS”) resin is known as an engineering plastic having excellent heat resistance and chemical resistance. For this reason, various studies have been made on the use of compositions with other thermoplastic resins and curable resins as electric / electronic components, taking advantage of these excellent features. For example, when a molded body such as a casing is injection-molded with a PAS resin composition and then applied to an electric / electronic component obtained by sealing with an epoxy resin, a conductor is mounted and fixed in the PAS resin casing. There is known an example in which an uncured epoxy resin is poured later, and then the epoxy resin is cured by heating or the like to obtain an electric / electronic component.

  When PAS is used for such applications, in addition to the long-term heat resistance and chemical resistance inherent to PAS, it has excellent adhesion to epoxy resins over a long period of time, particularly under a wide range of operating temperatures. Even if an epoxy resin encapsulated part using a molded body is repeatedly used in a temperature range of, for example, about −40 ° C. to about 140 ° C., a performance that does not cause separation at the interface between the encapsulated epoxy resin and the PAS resin molded body is required. It is done. However, PAS resin is inherently inferior in adhesion to an epoxy resin, and is fragile even when reinforced with glass fiber or the like, and thus cannot be used in this application.

Therefore, a PAS resin composition containing an epoxy resin and an amorphous polymer containing an oxazoline group in order to dramatically improve the adhesion of the epoxy resin during cooling without impairing the excellent heat resistance and chemical resistance inherent in the PAS resin. As a result, it has become possible to significantly improve the crack resistance during a thermal shock by using an impact-modified resin in combination (Patent Document 1).
By the way, in recent years, electrical insulation that can withstand the increase in output and voltage of electric and electronic devices and the reduction in thickness of resin molded products due to miniaturization / lightening, especially in the thickness direction of resin molded products (perpendicular to creeping surfaces). It is desired to maintain an excellent insulating property that can withstand a high voltage for a long time.
However, the PAS resin composition described in Patent Document 1 cannot always provide an excellent insulation life in the thickness direction of the molded product, and has room for improvement.

JP 2000-103964 A

  Then, the subject which this invention tends to solve is providing the PAS resin composition which can improve the insulation lifetime with respect to the thickness direction of a molded article, and a molded article using this composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that polyarylene containing an epoxy resin (B), an oxazoline group-containing amorphous polymer (C), and a triazine skeleton-containing compound (D) as essential components. The present inventors have found that the sulfide resin composition can improve the insulation life in the thickness direction of the resin molded body and can maintain excellent insulation capable of withstanding a high voltage for a long period of time, thereby completing the present invention.

That is, the present invention
A polyarylene sulfide resin composition comprising, as essential components, a polyarylene sulfide resin (A), an epoxy resin (B), an oxazoline group-containing amorphous polymer (C), and a triazine skeleton-containing compound (D) ,
Molded product obtained by molding the polyarylene sulfide resin composition,
The present invention relates to an electronic / electrical part incorporating the molded product.

  ADVANTAGE OF THE INVENTION According to this invention, the PAS resin composition which can improve the insulation lifetime with respect to the thickness direction of a molded article, and a molded article using this composition can be provided.

  The polyarylene sulfide resin (A) used in the present invention is not particularly limited, but is represented by the general formula (1) [-Ar-S-] (wherein -Ar- is at least one carbon 6-membered). A repeating unit represented by (indicating a divalent aromatic group containing a ring) as a main structural unit, in particular, those containing 70 mol% or more of the structural unit represented by the general formula (1), It is preferable from the viewpoint of excellent heat resistance and chemical resistance. Among the structural units represented by the general formula (1), in particular, the general formula (2)

Polyphenylene sulfide (hereinafter abbreviated as “PPS”) having a repeating unit represented by formula (2) is preferred, and a polymer containing 70 mol% or more of a repeating unit represented by the general formula (2) is particularly preferable as a crystalline polymer. It is preferable from the viewpoint that sufficient strength, which is a characteristic of the above, can be obtained and toughness and chemical resistance are also excellent. Here, the copolymer component with the structural unit represented by the general formula (2) contained in the polyarylene sulfide resin (A) includes a meta bond, an ether bond, a sulfone bond, a sulfide as shown below. Examples include a ketone bond, a biphenyl bond, a substituted phenyl sulfide bond, a trifunctional phenyl sulfide, and a naphthyl bond. The content of the copolymer component is preferably less than 30 mol%, but the content in the case of containing a trifunctional or higher functional bond is preferably 5 mol% or less, and more preferably 3 mol% or less.

  In addition, the polyarylene sulfide resin (A) used in the present invention is particularly excellent in reactivity with the component (B) and the component (C), and can greatly improve the epoxy adhesion at the time of cooling. Is 10 μmol / g or less, ΔNaOH is 5 to 30 μmol / g, and (ΔNaOH−ΔHCl) ≧ 5 μmol / g, the dispersibility of the components (B) and (C) is good, and the epoxy during cooling Adhesiveness is further improved, which is preferable.

Here, ΔHCl, ΔNaOH, and (ΔNaOH−ΔHCl) are values measured as follows.
[Measuring method]
10 g of polyarylene sulfide resin (A) is added with 10 ml of 1 mol / l HCl and stirred, and then filtered. Then, washing with water is repeated until no more HCl is detected, and all the filtrate used in the washing with water is collected, and the HCl in the filtrate is titrated with NaOH, so that the number of moles of consumed HCl is ΔHCl. Next, the polyarylene sulfide resin (A) after washing with water is again dispersed in distilled water, and 10 ml of 1 mol / l NaOH is added thereto and stirred. Filter after stirring and repeat washing with water until no more NaOH is detected. All the filtrate used in the water washing is collected, and NaOH in the filtrate is titrated with HCl, so that the moles of consumed NaOH is ΔNaOH. ΔNaOH−ΔHCl is the difference between ΔNaOH and ΔHCl determined in this way.

  The polyarylene sulfide resin (A) has a terminal thiol group concentration of 5 to 50 μmol / g, good reactivity with the components (B) and (C), excellent dispersibility, and fluidity. It is preferable from the viewpoint of excellent properties and good moldability. That is, when it is 5 μmol / g or more, it is excellent in dispersibility, and when it is 50 μmol / g or less, it is excellent in fluidity.

  In addition, the measuring method of the terminal thiol group density | concentration in this invention can be quantified by the iodoacetamide method. Here, the iodoacetamide method means that the PAS resin is once all acidified with hydrochloric acid or the like to form thiol groups, and then iodine is generated by the reaction of all terminal thiol groups with iodoacetamide under heating, which is used for acidification. The terminal thiol group present in the polymer at the initial stage is calculated from the number of moles of acid removed and the number of moles of iodine determined by UV spectroscopy.

Specific examples of the measurement method include the following methods.
[Measuring method]
About 10 mg to 1 g of the powdered polymer sample is precisely weighed, put into a tightly-plugged test tube, 1 ml of acetone and 3 ml of pure water are added, and after further dilute hydrochloric acid and stirring, the filtrate separated by filtration is back titrated with an aqueous NaOH solution. The number of moles of hydrochloric acid consumed for terminal acidification is measured. Next, the polymer sample separated by filtration is washed with pure water for 30 minutes, added with 2.5 ml of acetone and 2.5 ml of an acetone solution consisting of 50 mmol of iodoacetamide, sealed, heated at 100 ° C. for 60 minutes, cooled with water, Then, the liquid phase part is separated and the absorbance at 450 nm (I2 absorbance) is measured using an ultraviolet absorptiometer. Using the calibration curve prepared for the model thiol compound “Cl—C ₆ H ₄ —SH” in advance, the total terminal thiol group concentration after acidification is calculated from the absorbance (the sample amount is the thiol group concentration in the acetone slurry). It is preferable to select appropriately so that the concentration is in the range of 0.1 to 0.3 mmol.) The number of moles obtained by subtracting the number of moles of hydrochloric acid spent for terminal acidification from the total terminal thiol group concentration after acidification is the terminal thiol group of the PAS resin to be obtained. Measurement is performed three times for the same powdery sample, and the average value of the terminal thiol group concentration is determined.

  The polyarylene sulfide resin (A) used in the present invention may have either a molecular structure that is substantially linear and does not have a branched or crosslinked structure, or a structure that has branched or crosslinked, but has a substantially linear structure. What has it is preferable from points, such as reactivity and compatibility.

The polymerization method of such a polyarylene sulfide resin (A) is not particularly limited, but as a polymerization by a nucleophilic substitution reaction, as a method 1, a method of reacting a halogen-substituted aromatic compound and an alkali sulfide. Specifically,
Method 1-1: Method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate,
Method 1-2: A method of reacting p-dichlorobenzene with sodium sulfide in a polar solvent,
Method 1-3: A method of reacting p-dichlorobenzene with sodium hydrosulfide and sodium hydroxide in a polar solvent,
Method 1-4: A method of polymerizing p-dichlorobenzene in a polar solvent in the presence of hydrogen sulfide and sodium hydroxide,
Further, as Method 2, a method of self-condensing a thiophenol such as p-chlorothiophenol in the presence of an alkali catalyst such as potassium carbonate or sodium carbonate or a copper salt such as copper iodide can be mentioned. Examples of the polar solvent that can be used in Method 1 include amide solvents such as N-methylpyrrolidone and dimethylacetamide, sulfolane, and the like.

  Examples of the polymerization by electrophilic substitution include a method of condensing an aromatic compound such as benzene with sulfur chloride in the presence of a Lewis acid catalyst by a Friedel-Crafts reaction (Method 3).

  Among these, the method 1-2 is preferable because the molecular weight of the polyarylene sulfide resin (A) is high and the yield is high. Specifically, N-methylpyrrolidone, dimethylacetamide, etc. A method of reacting sodium sulfide with p-dichlorobenzene in a sulfone solvent such as amide solvent or sulfolane is most suitable. In the method 1-2, it is preferable to add an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide in order to adjust the degree of polymerization.

  In addition, the polyarylene sulfide resin (A) preferably has a substantially linear structure from the viewpoints of reactivity, compatibility, and the like. A method for producing a PAS resin having a substantially linear structure is not particularly specified. For example, an alkali metal sulfide, a dihaloaromatic compound, and lithium acetate in an organic amide solvent such as N-methylpyrrolidone and dimethylacetamide. In a method of reacting an organic alkali metal carboxylate such as, or reacting an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent, a large amount of water is added during the polymerization reaction and simultaneously the polymerization temperature is raised. Examples of the production method include a water addition two-stage polymerization method.

The polyarylene sulfide resin (A) having a substantially linear structure that is preferably used in the present invention is particularly preferably one that has been washed after acid treatment.
The acid used in this acid treatment is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin (A), but acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propyl acid, etc. Among them, acetic acid and hydrochloric acid are preferably used. Examples of the acid treatment method include a method of immersing the polyarylene sulfide resin (A) in an acid or an acid aqueous solution. At this time, stirring or heating can be performed as necessary. For example, when acid treatment is performed with acetic acid, a sufficient effect can be obtained by immersing the PAS resin in an aqueous solution of pH 4 heated to 80 to 90 ° C. and stirring for 30 minutes. The acid-treated PAS resin is preferably washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.
In the acid treatment, the polyarylene sulfide resin (A) particles may be used, or the polyarylene sulfide resin (A) in a slurry state after polymerization may be directly subjected to the acid treatment.

  Next, the epoxy resin (B) used in the present invention is an indispensable component that dramatically improves the adhesion to the cured epoxy resin, and when the impact modifying resin (E) described later is used in combination. In addition, the dispersibility of the component (E) is significantly improved.

  Such an epoxy resin (B) is not particularly limited, and bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and bisphenol AD type epoxy resin, biphenyl Type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resin, phenol aralkyl epoxy resin, naphthol novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol Examples include novolak-type epoxy resins, naphthol-cresol co-condensed novolak-type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resin-type epoxy resins, biphenyl novolac-type epoxy resins, etc. Among them, bisphenol-type epoxy resins, especially bisphenol A-type epoxy When resin is used, it is preferable because epoxy adhesiveness is remarkably improved. These epoxy resins (B) can be used alone or in combination of two or more.

  Specific examples of the bisphenol A type epoxy resin include glycidyl ether of bisphenol A and those having a structure in which the glycidyl ether is further polymerized with bisphenol A.

  As this epoxy resin (B), it is preferable that it is the range of 150-2100 g / eq of epoxy equivalent especially from the point that the moldability in a composition and compatibility are favorable. In particular, the range of 700 to 2100 g / eq is preferable from the viewpoint of moldability.

  Next, the oxazoline group-containing amorphous polymer (C) used as an essential component in the present invention drastically improves the adhesion to the cured epoxy resin as in the case of the component (B). This also improves the dispersibility of the impact-resistant modified resin (E). That is, in the present invention, by combining the component (B) and the component (C), an excellent epoxy adhesive property that has never been obtained is exhibited. Further, the oxazoline group-containing amorphous polymer (C) exhibits an effect in fine dispersion of the impact-resistant modified resin (E) in the PAS resin, and improves the thermal shock resistance of the entire resin composition. There is an effect.

  Here, the oxazoline group-containing amorphous polymer (C) is a state in which it is solidified by cooling from a state of being liquefied at a glass transition point or a temperature condition higher than the melting point, and is not within a temperature range of 200 ° C. or less. A polymer containing 80% by weight or more of crystal regions. Specific examples include a homopolymer of an oxazolinyl group-containing polymerizable unsaturated monomer, and a copolymer of the monomer and another polymerizable unsaturated monomer.

  Here, as the oxazolinyl group-containing polymerizable unsaturated monomer,

で示されるオキサゾリニル基含有不飽和モノマーを含有する共重合体である。ここでＸは、ラジカル重合可能な二重結合を有する置換基であり、次のものが挙げられる。

It is a copolymer containing the oxazolinyl group containing unsaturated monomer shown by these. Here, X is a substituent having a radically polymerizable double bond, and includes the following.

（式中、Ｒ_１は水素原子、炭素数１〜６のアルキル基またはアルコキシ基で、好ましくはメチル基、ｉ−またはｎ−プロピル基、ブチル基である。）。

(Wherein R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, preferably a methyl group, i- or n-propyl group or butyl group).

  The oxazolinyl group-containing polymerizable unsaturated monomer used in the present invention is preferably vinyl oxazoline. Here, as the vinyl oxazoline, for example,

（式中、Ｒ_２は水素原子またはメチル基）で示されるビニルオキサゾリンが挙げられる。

And vinyl oxazoline represented by the formula (wherein R ₂ is a hydrogen atom or a methyl group).

  Other polymerizable unsaturated monomers that can be copolymerized with the oxazolinyl group-containing polymerizable unsaturated monomer include, for example, aromatic vinyl such as styrene, vinyl cyanide such as acrylonitrile, vinyl acetate, and (meth) acrylic acid. , (Meth) acrylic acid esters, unsaturated carboxylic acids such as maleic anhydride or derivatives thereof, and α-olefins such as ethylene propylene, and diene components such as butadiene and isoprene. Of these, styrene and acrylonitrile are particularly preferred from the viewpoint of compatibility.

  In addition, the copolymer of the oxazolinyl group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer may be a binary copolymer or a ternary copolymer selected from the above monomer components. Specifically, vinyl oxazoline and styrene and / or acrylonitrile are preferable.

  In the present invention, in addition to the components (A) to (C) described above, the triazine skeleton-containing compound (D) is used in combination, so that the dielectric strength is excellent and the insulation lifetime in the thickness direction of the molded product is greatly improved. Can be improved. The triazine skeleton-containing compound (D) used in the present invention may be any compound having a triazine skeleton because the triazine skeleton expresses an improvement in the insulation life of the resin.

（式中、Ｒ_１、Ｒ_２、Ｒ_３は、アミノ基、アルキル基、フェニル基、ヒドロキシル基、ヒドロキシルアルキル基、アルキルアミノ基、エーテル基、エステル基、酸基、不飽和基、シアノ基、ハロゲン原子および−ＮＨＣＨ_３ＯＨ基のいずれかを表す）で表わされる化合物、下記一般式（２）

(Wherein R ₁ , R ₂ and R ₃ are an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group, an alkylamino group, an ether group, an ester group, an acid group, an unsaturated group, a cyano group, A compound represented by the following formula (2): a halogen atom or a —NHCH ₃ OH group)

（式中、Ｒ_４、Ｒ_５、Ｒ_６は、水素原子、アルキル基、フェニル基、ヒドロキシル基、ヒドロキシルアルキル基、エステル基、酸基、不飽和基、シアノ基、ハロゲン原子のいずれかを表す）で表される化合物、メラミンシアヌレート、トリアジン変性ノボラック型フェノール樹脂、メラミン樹脂が挙げられる。

(In the formula, R ₄ , R ₅ and R _{6 each} represent a hydrogen atom, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group, an ester group, an acid group, an unsaturated group, a cyano group or a halogen atom. ), A melamine cyanurate, a triazine-modified novolac phenol resin, and a melamine resin.

  Specific examples of the compound represented by the general formula (1) include triazine, melamine, guanamine derivatives such as acetoguanamine, benzoguanamine, and methylolmelamine, cyanuric acid, methyl cyanurate, ethyl cyanurate, acetyl cyanurate, cyanuric chloride. And cyanuric acid derivatives.

  Specific examples of the compound represented by the general formula (2) include isocyanuric acid, methyl isocyanurate, ethyl isocyanurate, allyl isocyanurate, 2-hydroxyethyl isocyanurate, 2-carboxylethyl isocyanurate, chlorinated isocyanurate. Examples include isocyanuric acid derivatives such as acids.

  Melamine cyanurate is a reaction product of melamine and cyanuric acid, and is a compound represented by the following structural formula (3).

  In the melamine cyanurate represented by the above structural formula, the cyanuric acid moiety may be either enol type or ketone type.

  The triazine-modified novolak type phenol resin is a known one as long as it is a novolak resin having a structure in which the triazine skeleton structure represented by the general formula (1) or (2) and the phenol structure are randomly bonded via a methylene group. For example, triazine compounds such as triazine, melamine, benzoguanamine, and acetoguanamine and phenols such as phenol, bisphenol A, cresol, butylphenol, and phenylphenol and formaldehyde in the presence of a weak alkaline catalyst such as alkylamines or Co-condensation reaction near neutral in the absence of catalyst, or the triazine skeleton structure and phenol structure obtained by reacting alkyl etherified products of triazine compounds such as methyl etherified melamine with phenols, etc. And a methylene group in the molecule, novolak resins substantially devoid of methylol groups. A molecule in which only the triazine skeleton structure is methylene-bonded, a molecule in which only the phenol structure is methylene-bonded, and a slight amount of unreacted monomer may be included unintentionally. Examples of commercially available triazine-modified novolak type phenol resins include “Phenolite KA-7052-L2”, “Phenolite LA-7052”, “Phenolite LA-7054”, “Phenolite LA-7751”, “Phenolite LA-1356”. "," Phenolite LA-3018-50P "(all manufactured by DIC Corporation), and the like.

  As the melamine resin, various alkylamines, methylol type, imino type, semi-cured type, methylol / imino type melamine resins and melamine oligomer condensates, which are commercially available from various manufacturers, can be used. Examples of commercially available melamine resins include “Coating Resin CL Transparent 20” (manufactured by Taiwa Co., Ltd.), “Super Becamine L-164” (manufactured by DIC Corporation), and “Super Becamine L-152-60” (DIC). Butyl etherified melamine resins such as “My Coat 506” (Mitsui Cytec Co., Ltd.), “My Coat 508” (Mitsui Cytec Co., Ltd.), “Cymel 303” (Mitsui Cytec Co., Ltd.), “ Methyl such as “Cymel 325” (Mitsui Cytec Co., Ltd.), “Cymel 327” (Mitsui Cytec Co., Ltd.), “Cymel 350” (Mitsui Cytec Co., Ltd.), “Nikarak MS15” (Sanwa Chemical Co., Ltd.) Etherified melamine resin; “Cymel 266” (Mitsui Cytec Co., Ltd.), “Cime "267" (manufactured by Mitsui Cytec Co., Ltd.), "Cymel 272" (manufactured by Mitsui Cytec Co., Ltd.), "Cymel 202" (manufactured by Mitsui Cytec Co., Ltd.), "Nikarak MXP485" (manufactured by Sanwa Chemical Co., Ltd.), "Nicarac MXP487 "Methyl / butyl mixed etherified melamine resin" (manufactured by Sanwa Chemical Co., Ltd.).

  Of the above-described triazine skeleton-containing compounds, melamine cyanurate, cyanuric acid, and melamine resin are preferable, and melamine cyanurate is more preferable because the above-described insulation life can be significantly improved. These compounds are not limited to one type in use, and two or more types can be used in combination.

  Although it does not restrict | limit especially as a content rate of each above-mentioned component in the resin composition of this invention, It is an epoxy resin with respect to 100 mass parts of polyarylene sulfide resin (A) with respect to the sum total of a resin composition. B) is 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, the oxazoline group-containing amorphous polymer (C) is 1 to 100 parts by mass, more preferably 3 to 20 parts by mass, and the triazine skeleton A containing compound (D) is 1-50 mass parts, More preferably, it is 5-30 mass parts. Within this range, the effect of the present invention becomes remarkable, and in a particularly preferable range, the effect of excellent insulation life in the thickness direction can be exhibited while maintaining the epoxy adhesive strength of the molded product.

  Although the mechanism of action of the resin composition of the present invention showing an excellent electrical insulation life is not clear at present, the triazine skeleton in the triazine skeleton compound decomposes first when voltage is continuously applied to the resin composition. Incombustible gas is generated, and by diluting the oxygen concentration in the atmosphere, the deterioration reaction to the PAS resin due to oxygen in the atmosphere is suppressed, and the electrical insulation life of the resin composition itself is improved. Yes.

  In the present invention, in addition to the components (A) to (D) described above, the toughness of the molded product is drastically improved by using the impact resistance modified resin (E) in combination, and the epoxy adhesion is improved. In addition to the drastic improvement, as described above, the crack resistance during thermal shock can be greatly improved.

  The impact-resistant modified resin (E) is not particularly limited, but in particular, an acid group or epoxy group-containing vinyl polymer (E1) and an acid group or epoxy group-containing rubbery polymer ( E2) is preferable from the viewpoint of excellent crack resistance against thermal shock.

  Further, the acid group or epoxy group-containing vinyl polymer (E1) is not particularly limited, but the acid group or epoxy group-containing α-polyolefin (E1-1), or the acid group or epoxy group-containing α, β- An unsaturated carboxylic acid alkyl ester polymer (E1-2) is mentioned.

  Here, the acid group or epoxy group-containing α-polyolefin (E1-1) is not particularly limited, but is an α-olefin, a copolymer of an α, β-unsaturated carboxylic acid or its anhydride, and an α-olefin. , Α, β-unsaturated carboxylic acid or anhydride thereof, and α, β-unsaturated carboxylic acid alkyl ester copolymer, α-olefin, and α, β-unsaturated carboxylic acid glycidyl ester copolymer , Α-olefin, α, β-unsaturated carboxylic acid glycidyl ester, and α, β-unsaturated carboxylic acid alkyl ester copolymers.

  Here, examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene-1, 4-methylpentene-1, and a mixture thereof. However, ethylene is particularly preferable.

  Examples of the α, β-unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, ethacrylic acid, cretonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid, and anhydrides thereof. In particular, maleic anhydride and succinic anhydride are preferably used.

  Next, the α, β-unsaturated carboxylic acid glycidyl ester is specifically glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, or the like, and glycidyl methacrylate is particularly preferably used.

  Examples of the α, β-unsaturated carboxylic acid alkyl ester include unsaturated carboxylic acids having 3 to 8 carbon atoms, such as alkyl esters such as acrylic acid, methacrylic acid, and ethacrylic acid. Specifically, acrylic acid Methyl, ethyl acrylate, acrylate-n-propyl, isopropyl acrylate, acrylate-n-butyl, acrylate-t-butyl, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, Examples thereof include isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid-t-butyl, and isobutyl methacrylate. Among these, methyl acrylate, ethyl acrylate, and acrylate-n-butyl are particularly preferable.

  The modification ratio of each monomer component with respect to the α-olefin is not particularly limited, but the modification site in the copolymer is converted to the weight of each monomer, and the ratio to the copolymer weight is as follows. In the case of α, β-unsaturated carboxylic acid or its anhydride, it is preferably 10% by weight or less, preferably 0.1 to 5% by weight, and in the case of α, β-unsaturated carboxylic acid glycidyl ester, A range of 0.1 to 15% by weight, particularly 0.5 to 10% by weight is preferable. Moreover, when using together alpha, beta-unsaturated carboxylic acid alkylester, the range of 5-35 weight% is preferable.

  Next, the acid group or epoxy group-containing α, β-unsaturated carboxylic acid alkyl ester polymer (E1-2) has a structure in which an acid group or an epoxy group is introduced into the α, β-unsaturated carboxylic acid alkyl ester polymer. Specifically, α, β-unsaturated carboxylic acid alkyl ester was copolymerized with α, β-unsaturated carboxylic acid or its anhydride or α, β-unsaturated carboxylic acid glycidyl ester. Examples include structures.

  Here, as the α, β-unsaturated carboxylic acid alkyl ester, any of those described above can be used, for example, an unsaturated carboxylic acid having 3 to 8 carbon atoms, specifically methyl acrylate, ethyl acrylate. , -N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, methacryl Examples thereof include alkyl esters such as acrylic acid such as acid-n-butyl, tert-butyl methacrylate, and isobutyl methacrylate, and methacrylic acid and ethacrylic acid. These may be used alone or in combination. . Of these, methyl acrylate, ethyl acrylate, and acrylate-n-butyl are particularly preferable.

  Next, α, β-unsaturated carboxylic acid or its anhydride to be copolymerized with these α, β-unsaturated carboxylic acid alkyl esters includes acrylic acid, methacrylic acid, ethacrylic acid, critonic acid, maleic acid, fumaric acid. Examples thereof include acid, itaconic acid, citraconic acid, butenedicarboxylic acid and anhydrides thereof, and maleic anhydride and succinic anhydride are particularly preferable.

  Further, α, β-unsaturated carboxylic acid glycidyl ester copolymerized with α, β-unsaturated carboxylic acid alkyl ester specifically includes glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like. In particular, glycidyl methacrylate is preferably used.

  As a modification ratio of α, β-unsaturated carboxylic acid or its anhydride or α, β-unsaturated carboxylic acid glycidyl ester to be copolymerized with α, β-unsaturated carboxylic acid alkyl ester, In the case of α, β-unsaturated carboxylic acid or its anhydride, 0.01 to 10% by weight, especially 0. In the case of an α, β-unsaturated carboxylic acid glycidyl ester in the range of 05 to 5% by weight, a range of 0.1 to 15% by weight, particularly 0.5 to 10% by weight is preferable.

  Next, the acid group or epoxy group-containing rubbery polymer (E2) is not particularly limited. For example, a conjugated diene and an aromatic vinyl monomer containing an acid group or an epoxy group A hydrogenated product of the copolymer is preferred. Specifically, α, β-unsaturated carboxylic acid or its anhydride or α, β-unsaturated carboxylic acid glycidyl ester is grafted onto a hydrogenated copolymer of a conjugated diene and an aromatic vinyl monomer. Those having a polymerized structure may be mentioned.

  Here, the hydrogenated copolymer of conjugated diene and aromatic vinyl hydrocarbon is a block copolymer or random copolymer of conjugated diene and aromatic vinyl hydrocarbon, and at least 80% of the copolymer is a random copolymer. It has been reduced by hydrogenation. In this case, among them, a block copolymer of a conjugated diene and an aromatic vinyl hydrocarbon is preferably used. In the present invention, double bonds of aromatic nuclei are not included as unsaturated bonds reduced by hydrogenation.

  Here, examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, and among them, 1,3-butadiene and isoprene are preferable.

  Examples of the aromatic vinyl hydrocarbon include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, 1,3-dimethyl styrene, vinyl naphthalene, and among them, styrene is preferable.

  Specific examples of hydrogenated copolymers of conjugated dienes and aromatic vinyl hydrocarbons include styrene / butadiene / styrene triblock hydrogenated copolymers and styrene / isoprene / styrene triblock hydrogenated copolymers. Of these, a styrene / butadiene / styrene triblock hydrogenated copolymer is preferred from the standpoint of remarkable crack prevention effects.

  The α, β-unsaturated carboxylic acid or its anhydride to be graft-copolymerized to the hydrogenated copolymer described in detail is acrylic acid, methacrylic acid, ethacrylic acid, critonic acid, maleic acid, fumaric acid, itaconic acid, citracone Examples thereof include acid, butenedicarboxylic acid and anhydrides thereof, and maleic anhydride and succinic anhydride are particularly preferable.

  Specific examples of the glycidyl α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable.

  The acid group or epoxy group content in the hydrogenated product (E2) is not particularly limited, but the functional group content in the hydrogenated product (E2) is converted to the amount of raw material monomer. In the case of α, β-unsaturated carboxylic acid or its anhydride, the ratio to the hydrogenated product (E2) in the case is 0.01 to 10% by weight, especially 0.05 to 5% by weight. In the case of α, β-unsaturated carboxylic acid glycidyl ester, it is preferably in the range of 0.1 to 15% by weight, especially 0.5 to 10% by weight.

  Among the acid group or epoxy group-containing vinyl polymer (E1) and the acid group or epoxy group-containing rubber polymer (E2), those having an acid group as a functional group are particularly suitable for epoxy adhesion and resistance. This is particularly preferable from the viewpoint of excellent cracking properties, and in particular, an acid group-containing vinyl polymer (E1), especially an acid group-containing α-olefin (E1-1), especially an α-olefin and an α, β-unsaturated carboxylic acid. A copolymer of an acid or an anhydride thereof and an α, β-unsaturated carboxylic acid alkyl ester is preferable because the effect is remarkable.

  The content ratio of the component (E) in the composition of the present invention is not particularly limited. However, in the resin composition, 0 part by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). By adding in an exceeding range, the effect of improving epoxy adhesion and crack resistance at the time of thermal shock can be exhibited, but it is further 0.5 to 100 parts by mass, more preferably 5 to 100 parts by mass. The range is preferable because the epoxy adhesion and crack resistance improvement of the present invention become more remarkable.

  In the present invention, it is preferable to further contain a fibrous reinforcing material (F) in addition to the components (A) to (D) or the components (A) to (E).

  The fibrous reinforcing material (F) is suitably used for improving crack resistance during cold heat. By including the fibrous reinforcing material, the strength that can withstand the stress caused by the thermal expansion and contraction of the PAS resin itself during cold heating is developed. In addition, the generation of cracks in the PAS resin molded product during cold heat is further suppressed.

  The fibrous reinforcing material is not particularly limited as long as it achieves the object of the present invention and is suitable for use, but specifically, glass fiber, carbon fiber, zinc oxide whisker, asbestos fiber, silica fiber, aluminum borate whisker, silica Alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, potassium titanate fiber, inorganic fiber material of metal such as stainless steel, aluminum, titanium, copper, brass, aramid fiber, polyamide, fluorine Examples thereof include high melting point organic fibrous materials such as resins and acrylic resins, among which glass fibers are preferable.

  The addition amount of the fibrous reinforcing material (F) is not particularly limited, but the crack generation at the time of cooling can be suppressed by adding in a range exceeding 0 part by mass with respect to 100 parts by mass of the PAS in the resin composition. However, it is further preferably in the range of 1 to 200 parts by mass, and more preferably in the range of 5 to 100% by weight, since the generation of cracks during cooling can be remarkably suppressed.

  In addition, the composition of the present invention further contains a silane compound (G), so that the compatibility between the PAS resin (A) and the oxazoline group-containing polymer (C), and further the impact-modified resin (E) It is possible to further improve the compatibility. In particular, the silane compound (G) can finely disperse the impact-modified resin (E) in the PAS resin, and can drastically improve the impact resistance of the entire resin composition.

  As such a silane compound (G), any silane coupling agent containing an organic functional group and a silicon atom in the structure can be used. Among them, an alkoxysilane or phenoxysilane containing an epoxy group, an alkoxy containing an amino group. Silane or phenoxysilane, or alkoxysilane or phenoxysilane containing an isocyanate group is preferred. These may be used alone or in combination of two or more.

  As the epoxyalkoxysilane or epoxyphenoxysilane, a silane compound having one or more epoxy groups in one molecule and two or three alkoxy groups or phenoxy groups is preferable. For example, γ-glycidoxypropyltrimethoxy Examples thereof include silane, γ-glycidoxypropyltriphenoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane.

  As the aminoalkoxysilane or aminophenoxysilane, a silane compound having one or more amino groups in one molecule and having two or three alkoxy groups or phenoxy groups is preferable. For example, γ-aminopropyltriethoxysilane, γ -Aminopropyltrimethoxysilane, γ-aminopropyltriphenoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N- β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl -Γ-aminopropyltriethoxy Orchid, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

  The isocyanate alkoxysilane or isocyanatephenoxysilane is preferably a silane compound having one or more isocyanate groups in one molecule and two or three alkoxy groups or phenoxy groups. For example, isocyanatepropyltriethoxysilane, isocyanatepropyl Examples include triphenoxysilane, isocyanatepropyltrimethoxysilane, and isocyanatepropylmethylyldiethoxysilane.

  The addition amount of the silane compound (G) exerts the effect of improving the impact resistance of the entire resin composition by adding the silane compound (G) in a range exceeding 0 part by mass with respect to 100 parts by mass of the PAS resin. However, the range of 0.01 to 3.0% by weight is preferable because the effect of improving the impact resistance becomes remarkable.

  In the composition of the present invention, in addition to each of the above components, a higher fatty acid ester (H) of a polyhydric alcohol is used in combination with a role as a mold release agent that improves mold release from the mold, and a resin. It is preferable from the point which improves the adhesiveness with the epoxy resin of a composition.

  The polyhydric alcohol mentioned here refers to an alcohol having two or more hydroxy groups in the molecule, and the higher fatty acid is preferably a saturated fatty acid or unsaturated fatty acid having 8 to 45 carbon atoms.

  Specific examples of the higher fatty acid ester (H) of polyhydric alcohol include caprylic acid, lauric acid, myristic acid, behenic acid, stearic acid, montanic acid, oleic acid and palmitic acid, ethylene glycol, glycerin, 2-Methylpropane-1.2.3. -Esters with polyhydric alcohols such as triol and pentaerythritol, and branched polyester oligomers thereof.

  The amount of the higher fatty acid ester (H) of the polyhydric alcohol added to the polyarylene sulfide resin (A) 100 parts by mass exceeds 0 part by mass, so that the mold releasability, the composition and Although the effect of improving the adhesiveness with the epoxy resin is exhibited, the range of 0.01 to 10 parts by mass is preferable because the release property and the adhesiveness with the epoxy resin become more remarkable.

  Furthermore, ethylene glycol and 2-methylpropane-1.2.3. Are preferable in that they have excellent thermal decomposition resistance to withstand the high processing temperature of the PAS resin. -Montolates of triols or pentaerythritol and their branched polyester oligomers can be added.

  Moreover, the composition of this invention may use together an inorganic filler in the range which does not impair the objective of this invention. Inorganic fillers include silicon carbide, boron nitride, various metal powders, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, nepheline cinteite, talc, talpulgite, wollast Knight, PMF, ferrite, aluminum oxalate, calcium oxalate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, alumina, magnesium oxide, magnesium hydroxide, iron oxide, molybdenum disulfide, graphite, Examples thereof include gypsum, glass beads, glass powder, glass balloons, quartz, silica, and quartz glass.

  The composition of the present invention can be used by mixing the following other polymers as long as the object of the present invention is not impaired. Examples of other polymers include monomers such as ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, and (meth) acrylonitrile. Homopolymer or copolymer, polyester such as polyurethane, polybutylene terephthalate, polyethylene terephthalate, polyacetal, polycarbonate, polyamide, polysulfone, polyallyl sulfone, polyether sulfone, polyarylate, polyphenylene oxide, polyether ketone, Polyetheretherketone, polyimide, polyamideimide, polyetherimide, silicone resin, phenoxy resin, fluororesin, liquid crystal polymer, polyaryl ether Homopolymer, random copolymer or block copolymer, can be mentioned graft copolymers.

  Moreover, you may add a plasticizer, a small amount of mold release agents, a coloring agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a rust preventive agent, a flame retardant, etc. to the composition of this invention.

  The composition of the present invention can be prepared by a known method. For example, a PAS resin (A), a bisphenol A type epoxy resin (B), an oxazoline group-containing polymer (C), and a triazine skeleton-containing compound (D), and if necessary, an impact-modified resin (E) and Other raw materials (for example, components (F to H)) are uniformly mixed with a mixer such as a tumbler or a Henschel mixer, and then supplied to a single or twin screw extrusion kneader to be in a temperature range of 200 ° C to 350 ° C. The method of melt-kneading below and obtaining the composition of this invention as a pellet is mentioned.

  The composition of the present invention is particularly excellent in adhesion to an epoxy resin cured product, but the epoxy resin cured product referred to here is a cured product obtained by curing reaction of a thermosetting epoxy resin and a curing agent. is there.

  Here, examples of the epoxy resin include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolmethane, and halogen substitution thereof. Body and alkyl group-substituted products, glycidyl ethers synthesized from compounds containing two or more hydroxyl groups in the molecule, such as butanediol, ethylene glycol, erythritol, novolak, glycerin, polyoxyalkylene, and epichlorohydrin, phthalates Glycidyl esters such as acid glycidyl ester, primary or secondary aniline, diaminodiphenylmethane, metaxylylenediamine, 1,3-bisaminomethylcyclohexane, etc. Glycidyl amine synthesized from amine and epichlorohydrin, glycidyl epoxy resins and the like such as, epoxidized soybean oil, vinylcyclohexene dioxide, non-glycidyl epoxy resins such as dicyclopentadiene dioxide and the like. These epoxy resins are used alone or as a mixture of two or more.

  Also, as described above, these epoxy resins are used after being cured with a curing agent. As described above, in applications where electronic components and various elements are encapsulated with an epoxy resin, for example, an uncured epoxy resin and a curing agent are mixed. Generally, it is poured into a post-PAS resin casing, and then the epoxy resin is cured by heating or the like. Examples of the curing agent include amines, polyamides, amino resins, acid anhydrides, polyhydric phenols, phenol resins, polysulfides, and isocyanates.

  The molded body using the PAS resin composition of the present invention not only has an insulation characteristic of the surface of the molded body (creeping direction) such as tracking resistance and an excellent insulation life in the thickness direction of the molded body, but also during thermal shock. Excellent mechanical properties such as crack resistance and impact resistance, and excellent adhesion strength with epoxy resin. For this reason, the PAS resin composition of the present invention can be used for various applications due to its excellent characteristics, such as excellent crack resistance and impact resistance, as well as electric / electronic parts and semiconductor parts. It can be used not only as a solution-type adhesive, paint, etc., but also as a case / part when an epoxy resin is used as a sealing material.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples. In addition, the part in an example means a weight part. In addition, the measurement of the terminal thiol group density | concentration, logarithmic viscosity [(eta)], melt flow rate, and total sodium content of PPS obtained by the following reference examples is as follows.

(1) Terminal thiol group concentration Conforms to the aforementioned iodoacetamide method.

(2) Logarithmic viscosity [η]
The relative viscosity value of an α-methylchloronaphthalene solution of PPS (PPS concentration 0.4 g / 100 ml) at 206 ° C. (400 ° F.) was measured, and based on the following formula: [η] = ln (relative viscosity value) / PPS concentration Calculation.

(3) Melt flow rate Value according to ASTM D1238 at 316 ° C./5000 g load, orifice; 0.0825 ± 0.002 inch diameter × 0.315 ± 0.001 inch length.

(4) Total sodium content Measured by atomic absorption method after decomposing the polymer with sulfuric acid.

(5) ΔHCl, ΔNaOH
10 g of the polymer is added with 10 ml of 1 mol / l HCl and stirred and then filtered. Then, washing with water is repeated until HCl is no longer detected (until AgNO ₃ solution is added dropwise to become cloudy), and all the filtrate used in washing with water is collected. The HCl in the filtrate is titrated with NaOH, and the amount of consumed HCl is reduced. The number of moles was ΔHCl. Next, the polyarylene sulfide resin (A) after washing with water is again dispersed in distilled water, and 10 ml of 1 mol / l NaOH is added thereto and stirred. After stirring, the mixture is filtered, and washing with water is repeated until no NaOH is detected (until the phenolphthalein solution is dropped to turn red). All the filtrate used in the water washing was collected, and NaOH in the filtrate was titrated with HCl, and the mole number of consumed NaOH was ΔNaOH.

Reference Example 1 (Production of PPS)
In a 5 l autoclave equipped with a stirrer, 1233 g of N-methylpyrrolidone, 636 g of sodium sulfide 2.7 g (5.0 mol, analysis 61.5%), lithium acetate dihydrate 510 g (5.0 mol) and water 90 g (5.0 mol) was charged, and 290 ml of a distillate containing 257 g of water was produced while stirring at 205 ° C. for about 1 hour and 20 minutes under a nitrogen atmosphere. Next, after cooling the reaction system to 150 ° C., a solution in which 750 g (5.1 mol) of p-dichlorobenzene was dissolved in 400 g of N-methylpyrrolidone was added and reacted at 265 ° C. for 3 hours. The internal pressure at the end of the polymerization reaction was 9.0 kg / cm ² . After that, the autoclave is cooled and the contents are filtered off. The cake is then washed three times with hot water and then twice with acetone, then immersed in an aqueous HCl solution at pH 1 for 30 minutes at room temperature, and then deionized. Washing with water / drying under reduced pressure at 80 ° C. gave 467 g of PPS. (Yield = 86%)
The PPS obtained here has a terminal thiol group concentration of 35 μmol / g, intrinsic viscosity [η] 0.25, a melt flow rate of 550 g / 10 minutes, a total sodium content of 100 ppm, ΔHCl = 1.0 μmol / g, ΔNaOH = 12.0 μmol / g. This was used as PPS.

Examples 1-10
The PPS resin produced in the above Reference Example 1 and each compounding component shown in Tables 1 to 2 are uniformly mixed in the proportions shown in the table, and then melt-kneaded at 300 ° C. in a 35 mmφ twin screw extruder. Pellets were obtained. The pellets were molded and test pieces for evaluation of various properties using an inline screw type 3 ounce injection molding machine at a cylinder temperature of 300 ° C., a mold temperature of 140 ° C., an injection pressure of 1000 kgf / cm ² , and an injection speed of medium speed. Various characteristics were evaluated. The results are shown in Tables 1 and 2. As the glass fiber, a chopped strand having a diameter of 10 μm was used. The evaluation items are as follows.

<Measurement of insulation life in penetration (thickness) direction>
In accordance with JIS-C2110-1994 measurement method of dielectric breakdown strength (7.1 (1)), the time [h] (when the AC voltage of 25 [KV] / 50 [Hz] is applied and conducted. Hereinafter, the conduction time [h]) was measured, and the insulation life in the thickness direction of the material was evaluated. However, the insulation life in the thickness direction of Examples 1 to 5 was expressed as a magnification when the insulation life of Comparative Example 1 was 1 (reference value).
Insulation life = (conduction time [h] in Examples 1 to 5) / (conduction time [h] in Comparative Example 1)

In Tables 1 and 2, numerical values in parentheses of components (A) and (D), and numerical values of components (B), (C), (E) and glass fibers (F) represent parts by mass, Abbreviations are as follows.
Epoxy resin (B): bisphenol A type epoxy resin, epoxy equivalent 2000
Oxazoline-modified resin (C): Oxazoline / styrene / acrylonitrile copolymer containing 5% by weight of vinyloxazoline (styrene / acrylo / tris = 70/25)

Triazine skeleton-containing compound (D1): Melamine cyanurate triazine skeleton-containing compound (D2): Melamine triazine skeleton-containing compound (D3): Cyanuric acid triazine skeleton-containing compound (D4): Aminotriazine novolak resin (“Phenolite” manufactured by DIC Corporation) KA-7052-L2 ", softening point 80 ° C., hydroxyl group equivalent 120 g / eq)
Triazine skeleton-containing compound (D5): Melamine resin ("Coating Resin CL Transparent 20" manufactured by Taiwa Co., Ltd.)

Impact Resin (E): Maleic anhydride (Gaah) graft styrene / butadiene / styrene block hydrogenated copolymer (ethylene butene / styrene / Gaah = 68/30/2)

  From the results of Tables 1 and 2, it was also revealed that when the triazine skeleton-containing compound was blended, the insulation life in the thickness direction of the test piece was excellent.

Claims (9)

Triazine having 1 to 50 parts by weight of epoxy resin (B), 1 to 100 parts by weight of oxazoline group-containing amorphous polymer (C), and NH ₂ group or OH group with respect to 100 parts by weight of polyarylene sulfide resin (A) A polyarylene sulfide resin composition comprising 1 to 50 parts by mass of a skeleton-containing compound (D) as an essential component. Triazine skeleton-containing compound (D) is melamine, cyanuric acid, melamine cyanurate, preparative triazine-modified novolak type phenolic resin and polyarylene sulfide resin composition according to claim 1, wherein at least one member selected from the group consisting of melamine resin .   The polyarylene sulfide resin composition according to claim 1, further comprising an impact resistance improving resin (E) in addition to the components (A) to (D).   The impact resistance improving resin (E) is a resin component selected from an acid group or epoxy group-containing vinyl polymer (E1) and an acid group or epoxy group-containing rubber polymer (E2). The polyarylene sulfide resin composition described.   The polyarylene sulfide resin composition according to claim 1, further comprising a fibrous reinforcing material (F) in addition to the components (A) to (D).   The polyarylene sulfide resin composition according to claim 1, wherein the epoxy resin (B) is a bisphenol type epoxy resin.   The molded product obtained by shape | molding the polyarylene sulfide resin composition as described in any one of Claims 1-6.   An electronic / electrical part incorporating the molded article according to claim 7. Triazine having 1 to 50 parts by weight of epoxy resin (B), 1 to 100 parts by weight of oxazoline group-containing amorphous polymer (C), and NH ₂ group or OH group with respect to 100 parts by weight of polyarylene sulfide resin (A) A method for producing a polyarylene sulfide resin composition, comprising melt-kneading 1 to 50 parts by mass of a skeleton-containing compound (D) as an essential component.