JP5003640B2 - Polyarylene sulfide resin composition and composite comprising the same - Google Patents

Description

  The present invention relates to a polyarylene sulfide resin composition and a composite comprising the same. More specifically, the present invention relates to adhesiveness and adhesion composed of polyarylene sulfide, a polar group-containing polyethylene copolymer and triazine thiols. The present invention relates to an excellent polyarylene sulfide-based resin composition, and a composite having excellent adhesion and adhesion at an interface composed of a metal member and the polyarylene sulfide-based resin composition.

  Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and dimensional stability. Utilizing these excellent properties, it is widely used in electrical and electronic equipment members, automotive equipment members, OA equipment members, etc. Has been. In these applications, for example, composite products with metal products, ceramic products, and epoxy resin products tend to increase, and adhesion and adhesion tend to be regarded as important.

  However, compared to other engineering plastics such as polyamide, polycarbonate, polybutylene terephthalate, and polyacetal, polyarylene sulfide has greater adhesion to epoxy resin, heat aging resistance, toughness, impact resistance, etc. Because it is inferior, its use has been limited in many applications.

  Several attempts have been made to improve the adhesiveness of polyarylene sulfide. For example, (a) polyarylene sulfide, (b) copolymer polyester, and (c) olefin copolymer are blended. Resin composition (for example, refer to Patent Document 2), (a) polyarylene sulfide, (b) bisphenol A type epoxy resin, (c) oxazoline group-containing amorphous polymer. ) Etc. have been proposed.

  Further, with regard to attempts to improve the toughness, impact resistance, etc. of polyarylene sulfide, for example, a resin composition comprising (a) polyarylene sulfide, (b) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer Product (for example, see Patent Document 3), (a) a composition obtained by melt-kneading polyphenylene sulfide and a non-blocking polyfunctional isocyanate compound, and (b) an ethylene-α, β-unsaturated carboxylic acid alkyl ester system. (A) polyarylene sulfide, (b) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, and (a) a resin composition containing the copolymer (for example, see Patent Document 4). c) A resin composition (for example, see Patent Document 5) composed of a specific type of alkoxysilane compound has been proposed.

  In addition, the use of a metal and a resin integrated as a composite is performed in various industries, and research and development of an adhesive suitable for the composite has been performed.

  On the other hand, in order to promote the simplification of the process and the number of parts when forming a composite, a method of integrally forming a metal and a resin without using an adhesive has been studied.

  Among such resins, polyphenylene sulfide (hereinafter also abbreviated as PPS) has excellent mechanical properties, thermal properties, and electrical properties, such as capacitor dielectrics, electrical insulating materials, Widely used in electronic parts and acoustic diaphragms. However, PPS has a problem that it has poor adhesion to metal and is not suitable for integral molding with metal.

  Therefore, an attempt to improve the adhesion to the resin by treating the surface of the metal has been proposed, and a method of forming a hole in the anodized film of the metal member and combining it with the resin has been proposed (for example, a patent). Reference 6). In addition, as a method for improving the adhesion between the thermoplastic resin and the metal part, a method of forming a thermoplastic resin by inserting a metal part subjected to chemical etching has been proposed (for example, see Patent Document 7).

Furthermore, a composite made of a metal and a polymer material subjected to electrochemical surface treatment with triazine thiols has been proposed (see, for example, Patent Documents 8 and 9).
Japanese Patent Laid-Open No. 11-228828 JP 2000-103964 A Japanese Patent Laid-Open No. 62-151460 Japanese Patent Laid-Open No. 02-255862 Japanese Patent Laid-Open No. 05-202245 Japanese Patent Laid-Open No. 2000-119889 WO2004-055248 JP 2001-225352 A Japanese Patent Laid-Open No. 02-298284 JP 2000-160392 A

  However, in the resin compositions proposed in Patent Documents 1 and 2, both the adhesiveness and the heat aging property of the adhesive strength are insufficient, and in the resin compositions proposed in Patent Documents 3 to 5, There was a problem that toughness, impact resistance and the like were not yet satisfactory. These proposals are all about the problem of improving the heat aging property of adhesiveness, adhesion and adhesive strength with epoxy resin, silicone resin, metal member, etc., and the problem of improving mechanical properties, heat cycle resistance, etc. Can not be satisfied at the same time. In the methods proposed in Patent Documents 6 and 7, there remains a problem in the adhesion between the metal part and the thermoplastic resin. Furthermore, the methods proposed in Patent Documents 8 and 9 require that the metal surface be subjected to electrochemical treatment, which requires complicated steps.

  Therefore, the present invention has high adhesion strength and adhesion strength with epoxy resin, silicone resin, metal member, etc. without impairing the heat resistance, chemical resistance, dimensional stability, etc. inherent to polyarylene sulfide, and those The purpose of the present invention is to provide a polyarylene sulfide resin composition that is excellent in heat aging, heat cycle resistance, and mechanical strength, and more specifically, electrical parts such as electrical / electronic parts or automotive electrical parts. An object of the present invention is to provide a polyarylene sulfide-based resin composition particularly useful for use and a composite comprising the same.

  As a result of intensive studies to solve the above problems, the present inventors have determined that an epoxy resin, a polyarylene sulfide resin composition comprising polyarylene sulfide, a specific polyethylene copolymer, and triazine thiols, The present invention has been completed by finding that it can be a composition having high adhesion strength and adhesion strength with silicone resin, metal members, etc., and excellent heat aging resistance, as well as heat cycle resistance and mechanical strength. I came to let you.

  That is, the present invention comprises polyarylene sulfide (A) 67-98.9% by weight, polar group-containing polyethylene copolymer (B) 1-30% by weight, and triazine thiols (C) 0.1-5% by weight. % Polyarylene sulfide-based resin composition.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide resin composition of the present invention comprises polyarylene sulfide (A) 67 to 98.9% by weight, polar group-containing polyethylene copolymer (B) 1 to 30% by weight, and triazine thiols (C). It consists of 0.1 to 5% by weight.

  As the polyarylene sulfide (A) constituting the polyarylene sulfide-based resin composition of the present invention, any polyarylene sulfide (A) may be used as long as it belongs to the category called polyarylene sulfide. Since the arylene sulfide resin composition is excellent in mechanical strength, toughness, impact resistance, weld strength, heat cycle resistance and molding processability, the measurement temperature is 315 ° C., the load is 10 kg, the diameter is 1 mm, A polyarylene sulfide having a melt viscosity of 100 to 30000 poise measured by a Koka flow tester equipped with a 2 mm long die is preferred, and a polyarylene sulfide having a melt viscosity of 200 to 20000 poise is particularly preferred.

  The polyarylene sulfide (A) preferably contains 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units as the structural unit.

  Other components include m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, diphenylene sulfide units, substituent-containing phenylene sulfide units, and branched structures. Phenylene sulfide units and the like. Among them, poly (p-phenylene sulfide) is a polyarylene sulfide resin composition having an excellent balance of adhesion, mechanical properties, heat cycle resistance, and mechanical strength. ) Is preferred.

  The method for producing the polyarylene sulfide (A) is not particularly limited, and may be produced by a method generally known as a method for producing polyarylene sulfide. For example, in a polymerization solvent, an alkali metal sulfide and It can be produced by a method of reacting with a dihaloaromatic compound. Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof, and these may be used in the form of hydrate. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base, and can be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system. It is possible to use one adjusted outside the system. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene. 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl ether, 4,4′-dichlorobenzophenone, 4,4′-dichlorodiphenyl, and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound = 1 / 0.9 to 1.1 (molar ratio).

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone. 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea and mixtures thereof. Moreover, it is preferable to use this polymerization solvent in 150-3500 weight% with respect to the polymer produced | generated by superposition | polymerization, and it is preferable to use especially in the range used as 250-1500 weight%. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Further, the polyarylene sulfide (A) may be a straight-chain one or a one obtained by treatment at high temperature in the presence of oxygen and crosslinked, and a slight amount of a polyhalo compound of trihalo or higher may be added to slightly crosslink or Even if it introduces a branched structure, it may be heat-treated in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures. Among these, as the polyarylene sulfide (A), the resulting polyarylene sulfide-based resin composition has an adhesiveness, adhesion, thermal aging resistance, and heat cycle resistance particularly with epoxy resins, silicone resins, metal members, and the like. Since it is excellent in balance, the functional group-containing polyarylene sulfide (a1) and / or linear polyarylene sulfide (a2) having a functional group corresponding to 0.05 to 5 mol% per arylene sulfide unit. Preferably there is.

  Examples of the functional group-containing polyarylene sulfide (a1) include amino group-containing polyarylene sulfide, carboxyl group-containing polyarylene sulfide, thiol group-containing polyarylene sulfide, and hydroxyl group-containing polyarylene sulfide. From the standpoint of easiness, amino group-containing polyarylene sulfides and carboxyl group-containing polyarylene sulfides are preferred.

  The functional group-containing polyarylene sulfide (a1) can be produced by a method in which, for example, when an alkali metal sulfide and a dihaloaromatic compound are reacted, polymerization is performed in the presence of the functional group-containing aromatic halogen compound. is there.

  Examples of the functional group-containing aromatic halogen compound include amino group-containing polyarylene sulfides such as 2,5-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, and 3,5-diamino. Chlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, 2,5-dibromoaniline, 2,6-dibromo Examples include aniline, 3,5-dibromoaniline, and mixtures thereof, and 3,5-dichloroaniline and 3,5-diaminochlorobenzene are particularly preferable. Examples of the carboxyl group-containing polyarylene sulfide include 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, and 2,6-dibromo. Examples include benzoic acid, 3,5-dibromobenzoic acid, and mixtures thereof, and 3,5-dichlorobenzoic acid is particularly preferable. When a thiol group-containing polyarylene sulfide is used, for example, 2,5-dichlorothiophenol, 2,6-dichlorothiophenol, 3,5-dichlorothiophenol, 2,5-dibromothiophenol, 2,6-dibromo Examples thereof include thiophenol, 3,5-dibromothiophenol, and mixtures thereof, and 3,5-dichlorothiophenol is particularly preferable. When the hydroxyl group-containing polyarylene sulfide is used, for example, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 2,5-dibromophenol, 2,6-dibromophenol, 3,5 -Dibromophenol and a mixture thereof are mentioned, and 3,5-dichlorophenol is particularly preferable.

  On the other hand, any linear polyarylene sulfide (a2) may be used as long as it belongs to the category called linear polyarylene sulfide. For example, it is described in JP-B-52-12240. It is possible to manufacture by this method.

  The polyarylene sulfide resin composition of the present invention comprises 67 to 98.9% by weight of polyarylene sulfide (A). Here, when the polyarylene sulfide (A) is less than 67% by weight, the resulting polyarylene sulfide-based resin composition has a significantly reduced mechanical strength. On the other hand, when it exceeds 98.9% by weight, the resulting polyarylene sulfide-based resin composition is inferior in adhesiveness, mechanical properties, and heat cycle resistance.

  The polar group-containing polyethylene-based copolymer (B) constituting the polyarylene sulfide-based resin composition of the present invention is combined with the triazine thiols (C), whereby the adhesiveness and adhesion of the polyarylene sulfide-based resin composition. In addition to improving their heat aging resistance and heat cycle resistance, the polar group-containing polyethylene copolymer is not particularly limited as long as it belongs to the category of polar group-containing polyethylene copolymers. Any one can be used, for example, a carboxylic acid group-containing polyethylene copolymer, a carboxylic acid ester group-containing polyethylene copolymer, an acid anhydride group-containing polyethylene copolymer, and a hydroxyl group-containing polyethylene copolymer. , Amino group-containing polyethylene copolymer, acetoxy group-containing polyethylene copolymer, epoxy -Containing polyethylene copolymer, oxazoline group-containing polyethylene copolymer, and the like. More specifically, for example, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene- ( (Meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, maleic anhydride graft-modified ethylene-α-olefin copolymer (b1), ethylene-α, β-unsaturated carboxylic acid alkyl ester Maleic anhydride copolymer (b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) And ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer b5) and the like. Among them, a maleic anhydride graft-modified ethylene-α-olefin copolymer is obtained because it becomes a polyarylene sulfide-based resin composition that is particularly excellent in adhesion, adhesion, and heat cycle resistance. (B1), ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5) Is preferred.

  Any maleic anhydride graft-modified ethylene-α-olefin copolymer (b1) may be used as long as it belongs to this category. Among them, the polyarylene sulfide resin composition obtained is adhesive. Since it is excellent in adhesion, thermal aging property and the like, ethylene residue unit: α-olefin residue unit: maleic anhydride residue unit (weight ratio) = 50 to 98:45 to 1: 5 to 1 Preferably, maleic anhydride graft-modified linear low-density polyethylene, maleic anhydride graft-modified ethylene-propylene rubber, and the like are mentioned. The maleic anhydride graft-modified ethylene-α-olefin copolymer (b1) is obtained, for example, by coexisting an ethylene-α-olefin copolymer, a peroxide, and maleic anhydride and proceeding with the grafting reaction. It is possible.

  As the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2), any copolymer may be used as long as it belongs to this category. Since the composition is excellent in adhesiveness, adhesiveness, thermal aging property and the like, ethylene residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) = It is preferable that it is the range of 50-98: 40-1: 10-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2) include (trade name) Bondine LX4110 (manufactured by Arkema), (trade name) Bondine TX8030 (Arkema). (Trade name) Bondine AX8390 (manufactured by Arkema) and the like.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), any copolymer belonging to this category may be used, and the polyarylene sulfide resin composition obtained is an adhesive. In the range of ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) = 85 to 99:15 to 1 It is preferable. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3) include (trade name) Bond Fast 2C (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) Bond Fast E ( Sumitomo Chemical Co., Ltd.).

  Any ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) may be used as long as it belongs to this category, and the polyarylene sulfide-based resin composition obtained among them may be used. Since the product is excellent in adhesiveness, adhesiveness, thermal aging property, etc., ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: vinyl acetate residue unit (weight ratio) = 50˜ It is preferable that it is the range of 98:15 to 1: 35-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) include (trade name) Bond Fast 2B (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) bond. Fast 7B (Sumitomo Chemical Co., Ltd.) etc. are mentioned.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5), any copolymer belonging to this category may be used. Since the resulting polyarylene sulfide-based resin composition is excellent in adhesiveness, adhesion, thermal aging property, etc., ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: α, β- The unsaturated carboxylic acid alkyl ester residue unit (weight ratio) is preferably in the range of 50 to 98:10 to 1:40 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5) include (trade name) Bondfast 7L (Sumitomo Chemical Co., Ltd.) Manufactured), (trade name) Bond Fast 7M (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Here, the α-olefin constituting the polar group-containing polyethylene copolymer (B) means an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1, Examples include hexene-1 and octene-1. Examples of the α, β-unsaturated carboxylic acid alkyl ester include alkyl esters such as acrylic acid and methacrylic acid, and specifically include methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. Isopropyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylic acid t- Examples include butyl. Examples of the α, β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

  The polyarylene sulfide resin composition of the present invention comprises 1 to 30% by weight of a polar group-containing polyethylene copolymer (B), and the blending amount of the polar group-containing polyethylene copolymer (B) is 1. When it is less than% by weight, the resulting polyarylene sulfide resin composition is inferior in adhesiveness, adhesion, heat aging resistance, and heat cycle resistance. On the other hand, when it exceeds 30% by weight, the resulting polyarylene sulfide-based resin composition has a significant decrease in mechanical strength.

  The triazine thiols (C) constituting the polyarylene sulfide resin composition of the present invention are compounded in combination with the polar group-containing polyethylene copolymer (B), so that the epoxy resin of the polyarylene sulfide resin composition is blended. In addition to improving the adhesive strength, adhesion strength, thermal aging properties of these, silicone resin, metal members, etc., and improving heat cycle resistance, it is in a category called triazine thiols. Any material can be used as long as it belongs, for example, 6-anilino-1,3,5-triazine-2,4-dithiol, 6-anilino-1,3,5-triazine-2,4- Dithiol monosodium, 6-dibutylamino-1,3,5-triazine-2,4-dithiol, 6-dibutylamino-1,3 5-triazine-2,4-dithiol monosodium, 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt, 6-diallylamino-1,3,5-triazine- 2,4-dithiol, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium, 6-dioctylamino-1,3,5-triazine-2,4-dithiol, 6-dioctyl Amino-1,3,5-triazine-2,4-dithiol monosodium, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol, 6-dilaurylamino-1,3,5 -Triazine-2,4-dithiol monosodium, 6-stearylamino-1,3,5-triazine-2,4-dithiol, 6-stearyl Mino-1,3,5-triazine-2,4-dithiol monosodium, 6-oleylamino-1,3,5-triazine-2,4-dithiol, 6-oleylamino-1,3,5-triazine Triazinedithiols (c1) such as 2,4-dithiol monopotassium; 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6-trithiol Monosodium, 1,3,5-triazine-2,4,6-trithiol-triethanolamine, 1,3,5-triazine-2,4,6-trithiol-di (tetrabutylammonium salt), etc. Among them, a polyarylene sulfide resin composition having excellent adhesion and adhesion to metals, epoxy resins, silicone resins, etc. Azindithiol (c1) is preferred.

  The polyarylene sulfide resin composition of the present invention comprises 0.1 to 5% by weight of triazine thiols (C), and is obtained when the blending amount of the triazine thiols is less than 0.1% by weight. The resulting polyarylene sulfide resin composition is inferior in adhesion, adhesion, heat aging resistance and heat cycle resistance. On the other hand, if it exceeds 5% by weight, the resulting polyarylene sulfide-based resin composition is remarkably reduced in moldability and mechanical strength.

  The polyarylene sulfide-based resin composition of the present invention preferably contains a lubricant (D) in order to improve mold releasability and appearance when forming a molded product. Examples of the lubricant (D) include carnauba wax (d1) and carboxylic acid amide wax (d2). As the carnauba wax (d1), a general commercially available product can be used, and examples thereof include (trade name) purified carnauba No. 1 powder (manufactured by Nikko Fine Products). The carboxylic acid amide wax (d2) is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine, and any one belonging to this category can be used. Examples thereof include (trade name) LIGHT AMIDE WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine.

  The blending amount of the lubricant (D) is unlikely to cause problems such as mold contamination particularly during molding processing, and becomes a polyarylene sulfide resin composition excellent in mold releasability and appearance of a molded product. The polyarylene sulfide (A), the polar group-containing polyethylene copolymer (B), and the triazine thiols (C) are preferably 0.05 to 5 parts by weight with respect to 100 parts by weight in total.

  The polyarylene sulfide-based resin composition of the present invention may contain an epoxy resin (E) for the purpose of further improving the adhesive strength, adhesion and thermal aging properties with an epoxy resin, silicone resin, metal member, and the like. it can. Any epoxy resin (E) may be used as long as it belongs to a category called an epoxy resin. Specific examples include 2,2-bis (4′-hydroxyphenyl) propane (sometimes referred to as bisphenol A), bis (2-hydroxyphenyl) methane (sometimes referred to as bisphenol F), 4, 4′-dihydroxydiphenylsulfone (sometimes referred to as bisphenol S), 4,4′-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted products thereof, and alkyl-substituted products thereof Glycidyl ether epoxy resin synthesized from a compound containing 2 or more hydroxyl groups in the molecule, such as butanediol, ethylene glycol, erythritol, novolak, glycerin, polyoxyalkylene, etc. and epichlorohydrin; In Glycidyl ester epoxy resin synthesized from a compound containing 2 or more and glycidyl phthalate, etc .; primary or secondary amine such as aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminomethylcyclohexane and epichloro Epoxy resins containing glycidyl groups such as glycidylamine-based epoxy resins synthesized from hydrin and the like, epoxy resins not containing glycidyl groups such as epoxidized soybean oil, epoxidized polyolefin, vinylcyclohexene dioxide, dicyclopentadiene dioxide, etc. Can be mentioned. Among them, the polyarylene sulfide-based resin composition obtained is particularly excellent in adhesion to epoxy resins, silicone resins, and metal members. Therefore, glycidyl ethers of bisphenols such as bisphenol A, bisphenol F, and bisphenol S are used. Bisphenol type epoxy resins such as epoxy resins and glycidyl ester epoxy resins are preferred. More preferred is a bisphenol A type epoxy resin.

  The compounding amount of the epoxy resin (E) is a polyarylene sulfide resin composition having excellent adhesion and adhesion to an epoxy resin, silicone resin, and metal member, so that polyarylene sulfide (A), polar It is preferable that it is 0.1-5 weight part with respect to a total of 100 weight part of group-containing polyethylene-type copolymer (B) and triazine thiols (C).

  The polyarylene sulfide-based resin composition of the present invention may be formed by blending a filler (F) blended in a general resin composition. As the filler (F), a fiber is used. Examples of the filler include glass fiber (f1), carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, stone-kow fiber, and metal fiber. Among them, glass fiber (f1) is preferable because it becomes a polyarylene sulfide-based resin composition particularly excellent in mechanical strength. Examples of non-fibrous fillers include silicates such as wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, talc, alumina silicate; aluminum oxide, silicon oxide, magnesium oxide, Oxides such as zirconium oxide, titanium oxide, zinc oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride and aluminum nitride Glass flakes, glass beads and the like can be exemplified, and among these, mica, clay, talc, calcium carbonate, glass flakes, and glass beads are preferable because the polyarylene sulfide resin composition is particularly excellent in dimensional stability. Moreover, since the filler (F) has high mechanical strength of the polyarylene sulfide-based resin composition, an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, etc. It may be surface-treated.

  Since the blending amount of the filler (F) is a polyarylene sulfide resin composition particularly excellent in mechanical strength and dimensional stability, the polyarylene sulfide (A), the polar group-containing polyethylene copolymer ( It is preferable that it is 10-150 weight part with respect to a total of 100 weight part of B) and triazine thiols (C).

  As a method for producing the polyarylene sulfide-based resin composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-400 degreeC. The polyarylene sulfide resin composition of the present invention can be molded into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

  Furthermore, the polyarylene sulfide-based resin composition of the present invention is a conventionally known heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent, mold corrosion prevention without departing from the object of the present invention. One or more additives such as an agent, a flame retardant, a flame retardant aid, a colorant such as a dye or pigment, and an antistatic agent may be used in combination.

  The polyarylene sulfide-based resin composition of the present invention is suitable for use as a composite with a metal, an epoxy resin, a silicone resin, and the like because it has excellent adhesion and adhesion. As the metal constituting the metal member at that time, any metal can be used as long as it belongs to the category of metals, among which aluminum, aluminum alloy, copper, copper alloy, magnesium, magnesium alloy, titanium, titanium alloy Stainless steel is preferable. In addition, since the metal member becomes a composite having excellent adhesion and adhesiveness at the interface with the polyarylene sulfide resin composition, the metal member is obtained by, for example, a chemical etching method, a physical surface roughening method, an anodizing method, or the like. It is preferable that the surface treatment is performed.

  The chemical etching method is a method in which surface roughening is performed by chemical treatment such as chemicals, and copper that is used to enhance the adhesion between a copper foil and a thermosetting epoxy resin in the production of a printed circuit board. Etching performed for the purpose of pre-decorating the metal surface in advance as a pre-decoration process in order to increase the adhesion of the paint to the metal material in the process of decorating the metal parts for the purpose of foil etching and decoration / rust prevention. For example, the methods described in JP-A-10-096088, JP-A-10-056263, JP-A-4-035855, and JP-A-04-032583 can be exemplified.

  The physical surface roughening method is a method of roughening the surface by physical means such as contacting or colliding fine solid particles with a metal surface or irradiating high-energy electromagnetic radiation, for example, sand blasting, This is known as a liquid honing process. Examples of the abrasive used in the sand blasting process and the liquid honing process include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, and plastic beads.

  The anodic oxidation method is a method in which a metal member is used as an anode to perform an electrification reaction in an electrolytic solution to form an oxide film on the surface thereof. A method generally known as an anodic oxidation method in the field of plating or the like is used. Examples thereof include 1) a DC electrolysis method in which electrolysis is performed by applying a constant DC voltage, and 2) a bipolar electrolysis method in which electrolysis is performed by applying a voltage in which an AC component is superimposed on a DC component.

  As a method for producing a composite comprising the polyarylene sulfide resin composition of the present invention, any method can be used as long as the composite can be produced. A member such as an epoxy resin member, a silicone resin member, or a metal member is mounted in a mold mounted on an injection molding machine, and the polyarylene sulfide-based resin composition is injected in a molten state to form a composite. It is preferable to manufacture by insert formation. Moreover, in that case, when it is a metal member, it is preferable that it is a member which roughened the surface by the above-mentioned method.

  The composite can be used for various applications that require these characteristics because the interface between the member and the polyarylene sulfide-based resin composition has good adhesiveness and adhesiveness. Examples include electrical equipment casings, electronic equipment parts, and electrical equipment parts. Furthermore, it is also suitable for electrical connection terminal parts such as sensors and coil bobbins.

  The polyarylene sulfide-based resin composition of the present invention has excellent adhesion and adhesion to metals, epoxy resins, and silicone resins, and has excellent mechanical properties, so that its industrial value is high.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  The polyphenylene sulfide, polyphenylene sulfide composition and composite used in the examples were evaluated and measured by the following methods.

-Measurement of melt viscosity of polyphenylene sulfide-
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka flow tester (manufactured by Shimadzu Corporation, (trade name) CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm. .

~ Measurement of amino group content ~
Using an infrared absorption spectrum measuring apparatus, the absorption at 1900 cm ⁻¹ (C—H out-of-plane vibration of the benzene ring) and the absorption at 3387 cm ⁻¹ (NH stretching vibration of an amino group) are measured. The amino group content was obtained. The calibration curve at that time was prepared from a mixture of benzene and aniline.

~ Evaluation of heat cycle resistance ~
The obtained composite was left at -25 ° C for 1 hour, heated to 150 ° C, left at 150 ° C, and then further cooled to -25 ° C for 100 cycles. Adhesiveness was evaluated based on the presence or absence of fracture at the interface.

~ Measurement of adhesive strength ~
The composite specimen was pulled at 5 mm / min with a tensile tester (manufactured by Shimadzu Corporation, (trade name) Autograph AG-5000B), and the breaking strength was measured. The breaking strength was divided by the bonding area to obtain the bonding strength.

<Synthesis Example 1 (Synthesis of polyphenylene sulfide (a1-2))>
A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone, and gradually heated to 205 ° C. while stirring under a nitrogen stream. 1355 g of water was distilled off. After cooling the system to 140 ° C., 7278 g of p-dichlorobenzene, 11.7 g of 3,5-dichloroaniline and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer is repeatedly washed with warm water and dried at 100 ° C. for a whole day and night, whereby an amino group-containing poly (p-phenylene sulfide) having a melt viscosity of 400 poise (hereinafter referred to as PPS (a1-1)) is obtained. Obtained. This PPS (a1-1) was further cured at 250 ° C. in an oxygen atmosphere for 2 hours to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter referred to as PPS (a1-2)).

  The melt viscosity of the obtained PPS (a1-2) was 1600 poise, and the amino group content per phenylene sulfide unit was 0.1 mol%.

<Synthesis Example 2 (Synthesis of polyphenylene sulfide (a2-1))>
A 50-liter titanium autoclave equipped with a stirrer was charged with 10773 g of N-methyl-2-pyrrolidone, 5607 g of 47% aqueous sodium hydrogen sulfide and 3807 g of 48% aqueous sodium hydroxide, and gradually heated to 200 ° C. while stirring under a nitrogen stream. Then, 4533 g of water was distilled off. The system was cooled to 170 ° C., 7060 g of p-dichlorobenzene and 5943 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C., polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. and polymerized at 250 ° C. for 2 hours. Further, 1503 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was carried out at 255 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation. The polymer was washed successively with N-methyl-2-pyrrolidone, acetone and water and dried overnight at 100 ° C. to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (a2-1)).

  The obtained PPS (a2-1) was linear, and its melt viscosity was 350 poise.

<Synthesis Example 3 (Synthesis of polyphenylene sulfide (a-2))>
A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone, and gradually heated to 205 ° C. while stirring under a nitrogen stream. 1355 g of water was distilled off. After the system was cooled to 140 ° C., 7160 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried at 100 ° C. for 24 hours to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (a-1)) having a melt viscosity of 280 poise. This PPS (a-1) was further cured at 250 ° C. for 4 hours in an oxygen atmosphere to obtain PPS (a-2).

  The melt viscosity of the obtained PPS (a-2) was 3000 poise.

<Synthesis Example 4 (Synthesis of maleic anhydride-modified linear low density polyethylene)>
250 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and dialkyl peroxide (manufactured by NOF Corporation), 10 kg of linear low density polyethylene (manufactured by Tosoh Corporation, (trade name) Nipolon Z 1P53A), (Product name) 10 g of Perhexa 25B was uniformly mixed with a hex shell mixer. Then, it was extruded at a cylinder temperature of 220 ° C. with a twin-screw extruder (Toshiba Machine Co., Ltd., (trade name) TEM-35-102B) to obtain maleic anhydride-modified linear low-density polyethylene. The maleic anhydride content obtained from a calibration curve prepared separately by measuring absorption by a carbonyl group by infrared absorption spectrum was 1.4 wt%. The melt flow rate (MFR) was 0.7 g / 10 min (measuring temperature 190 ° C., load 21.18 N).

Example 1
84% by weight of PPS (a1-2) obtained from Synthesis Example 1, 15% by weight of maleic anhydride-modified linear low density polyethylene obtained from Synthesis Example 4, and 6-anilino-1,3,5-triazine -100 parts by weight of 2,4-dithiol 1% by weight Carnauba wax (manufactured by Nikko Fine Products, (trade name) purified carnauba No. 1 powder) 0.5 parts by weight, 310 ° C To a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B). On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

The polyarylene sulfide-based resin composition pellets were put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) heated to 310 ° C., and an ASTM D-638 No. 1 dumbbell test piece was molded. The test piece was cut into two at the center of the dumbbell parallel part, and a two-part epoxy adhesive (manufactured by Nagase Chemtex Co., Ltd., (trade name) XNR5002 and XNH5002) with an adhesion area of 1.27 cm ² (test piece) The epoxy adhesive was cured at 100 ° C. × 1 hr and then 150 × 3 hr to prepare a test piece for evaluating epoxy adhesion.

  The epoxy adhesive strength obtained from the test piece for evaluating epoxy adhesion was as high as 16.1 MPa, and the fracture mode was cohesive failure.

  Aluminum alloy (A1050) test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) was subjected to surface roughening with # 200 sandpaper, and then immersed in ethanol to clean the surface. By performing this, a test piece made of a surface roughened aluminum alloy (A1050) was obtained.

  An injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) in which the aluminum alloy (A1050) test piece was mounted in an injection molding machine mold and the polyarylene sulfide resin composition pellets were heated to 310 ° C. The composite was obtained by inserting into a hopper of SE75) and performing insert molding.

  When the heat cycle resistance of the obtained composite was evaluated, the composite was not destroyed in 100 cycles of the low and high temperature resistance test. The adhesive strength was 5.8 MPa.

Example 2
87% by weight of PPS (a2-1) obtained from Synthesis Example 2, 12% by weight of ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine TX8030) % And 6 parts of 6-diallylamino-1,3,5-triazine-2,4-dithiol in a total amount of 100 parts by weight, carnauba wax (manufactured by Nikko Fine Products, (trade name) refined carnauba No. 1 (Powder) The mixture was added at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 20 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.7 MPa, and the fracture mode was cohesive fracture.

  After cleaning the surface by immersing an aluminum test piece (35 mm (long side) × 13 mm (short side) × 2 mm (thickness)) in ethanol, the test piece was immersed in an aqueous magnesium hydroxide solution, A surface-roughened aluminum test piece was obtained by chemical etching.

  The aluminum test piece was mounted in an injection molding machine mold, and a composite was obtained by the same method as in Example 1. When the composite was evaluated, the composite was tested in 100 cycles of the low and high temperature resistance test. There was no destruction. The adhesive strength was 6.1 MPa.

Example 3
PPS (a-2) 85% by weight obtained from Synthesis Example 3, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine AX8390) 14% %, And 6 parts of 6-anilino-1,3,5-triazine-2,4-dithiol monosodium in a total amount of 100 parts by weight, carnauba wax (manufactured by Nikko Fine Products, (trade name) refined carnauba No. 1 powder) was mixed at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 20 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.2 MPa, and the fracture mode was cohesive fracture.

  Using aluminum alloy (A5052) test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) with a liquid homing device, an alumina abrasive with a particle size of # 220, concentration of 15% by weight, gauge The surface was cleaned by spraying under a pressure of 0.6 MPa and then immersed in acetone to obtain a test piece made of a surface roughened aluminum alloy (A5052).

  The aluminum alloy (A5052) test piece was mounted in an injection molding machine mold, a composite was obtained by the same method as in Example 1, and evaluated using the composite. No destruction of the complex was observed. The adhesive strength was 5.4 MPa.

Example 4
84 wt% of PPS (a1-2) obtained from Synthesis Example 1, ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (manufactured by Sumitomo Chemical Co., Ltd., (trade name) Bondfast E) 14 wt% % And 6 parts of 6-dioctylamino-1,3,5-triazine-2,4-dithiol in a total amount of 100 parts by weight, carnauba wax (manufactured by Nikko Fine Products, (trade name) refined carnauba No. 1 (Powder) The mixture was added at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.1 MPa, and the fracture mode was cohesive fracture.

  After cleaning the surface by immersing a test piece (35 mm (long side) × 13 mm (short side) × 2 mm (thickness)) made of aluminum alloy (A1100) in methanol, the test piece was used as an anode at 20 ° C. Was immersed in an electrolytic solution having a hydrochloric acid concentration of 0.2 mol / liter, and anodization was performed by direct current electrolysis at a base voltage of 40 V for 30 minutes to obtain a test piece made of a surface roughened aluminum alloy (A1100).

  The aluminum alloy (A1100) test piece was mounted in an injection mold, a composite was obtained by the same method as in Example 1, and evaluated by the composite. No destruction of the complex was seen. The adhesive strength was 6.5 MPa.

Example 5
84% by weight of PPS (a1-2) obtained from Synthesis Example 1, 15% by weight of an ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, (trade name) Ultrasen 630), and 1,3,5- Carnava wax (manufactured by Nikko Fine Products, (trade name) refined carnava No. 1 powder) at a ratio of 0.5 part by weight to 100 parts by weight of the total amount consisting of 1% by weight of triazine-2,4,6-triazine trithiol. It mix | blended and it injected | thrown-in to the hopper of the twin-screw extruder (Toshiba machine make, (brand name) TEM-35-102B) heated to 310 degreeC. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 15.3 MPa, and the fracture mode was cohesive fracture.

  Aluminum alloy (A1100) test piece (35 mm (long side) × 13 mm (short side) × 2 mm (thickness)) was subjected to surface roughening with # 200 sandpaper, and then immersed in ethanol to clean the surface. By performing this, a test piece made of a surface-roughened aluminum alloy (A1100) was obtained.

  The aluminum alloy (A1100) test piece was mounted in an injection mold, a composite was obtained by the same method as in Example 1, and evaluated by the composite. No destruction of the complex was seen. The adhesive strength was 5.6 MPa.

Example 6
PPS (a-2) 85% by weight obtained from Synthesis Example 3, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine AX8390) 14% % And a total amount of 100 parts by weight of 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium, carnauba wax (manufactured by Nikko Fine Products, (trade name) Carnauba No. 1 powder) was mixed at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 20 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.3 MPa, and the fracture mode was cohesive fracture.

  By subjecting a copper test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) to surface roughening with # 200 sandpaper, and then immersing in ethanol, the surface is washed, A surface roughened copper test piece was obtained.

  When the copper test piece was mounted in an injection mold, a composite was obtained by the same method as in Example 1, and the composite was evaluated. The composite was destroyed in 100 cycles of the low and high temperature resistance test. I couldn't see it. The adhesive strength was 5.3 MPa.

Example 7
85% by weight of PPS (a1-2) obtained from Synthesis Example 1, 14% by weight of ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine AX8390) % And 6 parts of 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium in a total amount of 100 parts by weight, carnauba wax (manufactured by Nikko Fine Products, (trade name) Carnauba No. 1 powder) was mixed at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 20 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.1 MPa, and the fracture mode was cohesive fracture.

  Copper alloy (C1020) test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) was subjected to surface roughening with # 200 sandpaper, and then immersed in ethanol to clean the surface. By performing this, a surface-roughened copper alloy (C1020) test piece was obtained.

  The copper alloy (C1020) test piece was mounted in an injection mold, and a composite was obtained by the same method as in Example 1. The composite was evaluated. No destruction of the complex was seen. The adhesive strength was 5.6 MPa.

Example 8
PPS (a-2) 85% by weight obtained from Synthesis Example 3, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine AX8390) 14% %, And 100 parts by weight of 6-dioctylamino-1,3,5-triazine-2,4-dithiol monosodium in a total amount of 100 parts by weight, purified by carnauba wax (manufactured by Nikko Fine Products, (trade name) Carnauba No. 1 powder) was mixed at a ratio of 0.5 part by weight and charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 20 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to prepare polyarylene sulfide resin composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide-based resin composition pellets in the same manner as in Example 1, and the epoxy adhesion evaluation was conducted. Was as high as 16.1 MPa, and the fracture mode was cohesive fracture.

  Stainless steel (SUS304) test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) is subjected to surface roughening with # 200 sandpaper, and then immersed in ethanol to clean the surface. By performing this, a test piece made of surface roughened stainless steel (SUS304) was obtained.

  A test piece made of stainless steel (SUS304) was mounted in an injection mold, a composite was obtained by the same method as in Example 1, and evaluated using the composite. There was no destruction of the body. The adhesive strength was 4.8 MPa.

Comparative Example 1
Carnauba wax (based on 85 parts by weight of PPS (a1-2) obtained from Synthesis Example 1 and 15 parts by weight of maleic anhydride-modified linear low density polyethylene obtained from Synthesis Example 4 was 100 parts by weight. A twin screw extruder (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B) blended at a ratio of 0.5 parts by weight (made by Nikko Fine Products, (trade name) refined carnauba No. 1 powder) and heated to 310 ° C. Was put into the hopper. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to produce polyarylene sulfide composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide composition pellets in the same manner as in Example 1, and an epoxy adhesion evaluation was conducted. It was as low as .9 MPa, and the fracture mode was interfacial debonding.

  Aluminum alloy (A1050) test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) was subjected to surface roughening with # 200 sandpaper, and then immersed in ethanol to clean the surface. By performing this, a test piece made of a surface roughened aluminum alloy (A1050) was obtained.

  An injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) in which the aluminum alloy (A1050) test piece was mounted in an injection molding machine mold and the polyarylene sulfide composition pellets were heated to 310 ° C. Was inserted into a hopper and insert molded to obtain a composite.

  When the heat cycle resistance of the obtained composite was evaluated, the composite was destroyed in 10 cycles of the low and high temperature resistance test, so that the adhesive strength could not be obtained.

Comparative Example 2
For 100 parts by weight of the total amount of 99% by weight of PPS (a1-2) obtained from Synthesis Example 1 and 1% by weight of 6-anilino-1,3,5-triazine-2,4-dithiol, carnauba wax ( A twin screw extruder (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B) blended at a ratio of 0.5 parts by weight (made by Nikko Fine Products, (trade name) refined carnauba No. 1 powder) and heated to 310 ° C. Was put into the hopper. On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to produce polyarylene sulfide composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide composition pellets in the same manner as in Example 1, and an epoxy adhesion evaluation was conducted. It was as low as 0.5 MPa, and the fracture mode was interfacial debonding.

  By subjecting an aluminum test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) to surface roughening with sandpaper # 200, and then immersing it in ethanol to clean the surface. A surface-roughened aluminum test piece was obtained.

  The aluminum test piece is mounted in an injection molding machine mold, and the polyarylene sulfide composition pellets are put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75). Insert molding was performed to obtain a composite.

  When the heat cycle resistance of the obtained composite was evaluated, the composite was destroyed in 15 cycles of the low and high temperature resistance test, so that the adhesive strength could not be obtained.

Comparative Example 3
PPS (a-2) 85% by weight obtained from Synthesis Example 3, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (manufactured by Arkema, (trade name) Bondine AX8390) 14% % And N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) KBM-603) 1 wt% A twin screw extruder (manufactured by TOSHIBA MACHINE, (trade name) TEM-35, blended at a ratio of 0.5 parts by weight of wax (manufactured by Nikko Fine Products, (trade name) refined carnauba No. 1 powder) and heated to 310 ° C. 102B). On the other hand, glass fiber (manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91) is supplied from the side feeder of the twin screw extruder so as to be 25 parts by weight, and melted at a screw rotation speed of 200 rpm. The molten composition flowing out from the die was kneaded and cut after cooling to produce polyarylene sulfide composition pellets.

  An ASTM D-638 No. 1 dumbbell test piece and an epoxy adhesion evaluation test piece were prepared from the polyarylene sulfide composition pellets in the same manner as in Example 1. When the epoxy adhesion evaluation was performed, the epoxy adhesion strength was 7 The fracture mode was interfacial debonding, as low as 0.5 MPa.

  By subjecting an aluminum test piece (35 mm (long side) x 13 mm (short side) x 2 mm (thickness)) to surface roughening with sandpaper # 200, and then immersing it in ethanol to clean the surface. A surface-roughened aluminum test piece was obtained.

  The aluminum test piece is mounted in an injection molding machine mold, and the polyarylene sulfide composition pellets are put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75). Insert molding was performed to obtain a composite.

  When the heat cycle resistance of the obtained composite was evaluated, the composite was destroyed in 20 cycles of the low and high temperature resistance test, so that the adhesive strength could not be obtained.

Claims (5)

It comprises polyarylene sulfide (A) 67 to 98.9% by weight, polar group-containing polyethylene copolymer (B) 1 to 30% by weight, and triazinethiol (C) 0.1 to 5% by weight. A polyarylene sulfide-based resin composition. The polyarylene sulfide resin composition according to claim 1, wherein the triazine thiols (C) are triazine dithiols (c1). The polar group-containing polyethylene copolymer (B) is a maleic anhydride graft-modified ethylene-α-olefin copolymer (b1), ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer ( b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4), ethylene-α, β- It is at least one polar group-containing polyethylene copolymer selected from the group consisting of unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymers (b5). The polyarylene sulfide resin composition according to claim 1 or 2. Metal member selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, magnesium, magnesium alloy, titanium, titanium alloy and stainless steel and polyarylene sulfide (A) 67-98.9 wt%, polar group-containing polyethylene A composite comprising a polyarylene sulfide resin composition comprising 1 to 30% by weight of a copolymer (B) and 0.1 to 5% by weight of a triazine thiol (C). The composite according to claim 4, which is formed by an insert molding method.