WO2019208377A1 - Polyarylene sulfide resin composition, molded article, composite molded article, and method for producing foregoing - Google Patents

Abstract

Provided are: a molded article of a polyarylene sulfide (PAS) resin composition having excellent epoxy adhesiveness and thermal shock resistance, in particular not only the thermal shock resistance addressed when a welded part is included but also the thermal shock resistance in the transverse (TD) direction; a PAS resin composition that can provide said molded article; and a composite molded article made by bonding said molded article and a cured product of a curable resin composition including an epoxy resin; and a method for producing the foregoing. More specifically, provided are: a PAS resin composition resulting from blending a PAS resin, an epoxy resin, an epoxy group-containing polyolefin, glass fibers, and glass flakes, wherein, with respect to 100 parts by mass of the PAS resin, the content of the glass fibers is 10-350 parts by mass and the content of the glass flakes is 1-250 parts by mass, the total content of epoxy group included in the epoxy resin and the epoxy resin-containing polyolefin is 25-300 μmol per 1 g of the PAS resin composition, and the epoxy equivalent of the epoxy resin is 100-2,400 g/eq.; a molded article thereof; a composite molded article thereof; and a method for producing the foregoing.

Description

Polyarylene sulfide resin composition, molded article, composite molded article, and production method thereof

The present invention relates to a resin composition, a molded article, a composite molded article, and a method for producing them, including a polyarylene sulfide (hereinafter sometimes abbreviated as “PAS”) resin.

PAS resins represented by polyphenylene sulfide (hereinafter sometimes abbreviated as “PPS”) resins are excellent in mechanical strength, heat resistance, chemical resistance, moldability, and dimensional stability. It is used as electrical / electronic equipment parts, automotive parts materials, etc.

In many cases, these parts are bonded to a part material made of epoxy resin or the like as a secondary process. However, PAS resins have relatively poor adhesion to other resins, especially adhesion to epoxy resins. Therefore, for example, when bonding PASs with epoxy adhesives, bonding PAS resins with other materials, or sealing electrical / electronic parts with epoxy resins, the adhesion between PAS resins and epoxy resins (hereinafter referred to as “bonding”) In some cases, the problem of “adhesiveness” is a problem.

Further, since PAS resin is inferior in toughness, it has a problem that it is brittle with respect to a thermal cycle by repeated low and high temperatures, or thermal shock, and inferior in thermal shock resistance. Further, when reinforced with a fibrous reinforcing material such as glass fiber, anisotropy occurs, and a phenomenon such as warping or twisting occurs in the molded product, and the dimensional stability is not sufficient.

From such a current situation, several studies have been made so far for the purpose of improving the thermal shock resistance, dimensional stability, and adhesiveness of the epoxy resin of the PAS resin. For example, glass fiber, olefin polymer, epoxy resin A PAS resin composition containing glass flakes has been proposed (see Patent Document 1). However, since this method uses a bisphenol A type epoxy resin as an epoxy resin, it has excellent adhesiveness and fluidity with the epoxy resin, but the thermal shock resistance is at a level that is hardly sufficient for practical use.

Therefore, a molded body made of a PAS resin composition obtained by blending PAS resin, bisphenol-type epoxy resin, novolac-type epoxy resin, glass fiber, and glass flake and melting and kneading has been proposed (patent). Reference 2). The molded body was excellent in the thermal shock resistance even if it has an adhesiveness with an epoxy resin and a weld part, but there is still room for improvement in the thermal shock resistance, such as injection molding. There was still room for improvement in the thermal shock resistance in the direction perpendicular to the resin flow (TD direction) during melt molding.

JP 2005-306926 A WO2013 / 141363 pamphlet

Therefore, the problem to be solved by the present invention is a polyarylene sulfide resin which is excellent in epoxy adhesiveness and has excellent thermal shock resistance, in particular, thermal shock resistance in the case of having a weld part, as well as excellent thermal shock resistance in the TD direction. Molded product of composition, polyarylene sulfide resin composition capable of providing the molded product, and composite molded product obtained by bonding the molded product to a cured product of a curable resin composition containing an epoxy resin, and the same It is to provide a manufacturing method.

As a result of intensive studies to solve the above problems, the present inventor has found that polyarylene sulfide resin (A) and 100 [g / eq. ] 2400 [g / eq. ] An epoxy resin (B) having an epoxy equivalent weight in the following range, an epoxy group-containing polyolefin (C), glass fiber (D1) and glass flake (D2), and the amount of epoxy groups in the composition It has been found that the above-mentioned problems can be solved by setting the amount in the range of 25 [μmol] to 300 [μmol] in 1 g of the composition, and the present invention has been completed.

That is, the present invention provides a polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2). A thing,
With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber ranges from 10 parts by weight to 350 parts by weight, and the glass flake ranges from 1 part by weight to 250 parts by weight.
In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [μmol] to 300 [μmol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. ] It relates to a polyarylene sulfide resin composition in the following range.

The present invention also relates to a molded article formed by melt molding the polyarylene sulfide resin composition.

The present invention also provides a polyarylene sulfide resin composition in which a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2) are melt-kneaded. A manufacturing method of
With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber ranges from 10 parts by weight to 350 parts by weight, and the glass flake ranges from 1 part by weight to 250 parts by weight.
In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [μmol] to 300 [μmol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. The present invention relates to a method for producing a polyarylene sulfide resin composition in the following range.

Furthermore, this invention relates to the manufacturing method of the composite molded article which adhere | attaches the said molded article and the hardened | cured material of curable resin composition containing an epoxy resin.
Furthermore, this invention relates to the manufacturing method of a composite molded article including the process of making this curable resin composition contact after making the curable resin composition containing an epoxy resin contact.

According to the present invention, a molded article of a polyarylene sulfide resin composition having excellent epoxy adhesiveness and not only thermal shock resistance, particularly in the case of having a weld portion, but also excellent thermal shock resistance in the TD direction. Provided are a polyarylene sulfide resin composition capable of providing the molded article, a composite molded article obtained by bonding the molded article and a cured product of a curable resin composition containing an epoxy resin, and a method for producing the same. be able to.

In an Example, it is a metal block member used for the cold thermal shock resistance (heat cycle property) test of the TD direction of a molded article (without a weld part). In an Example, it is a molded article (without a weld part) used for the cold thermal shock resistance (heat cycle property) test of TD direction.

The polyarylene sulfide resin composition used in the present invention comprises a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2). A polyarylene sulfide resin composition comprising:
With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber ranges from 10 parts by mass to 350 parts by mass, the glass flake ranges from 1 part by mass to 250 parts by mass,
In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [μmol] to 300 [μmol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. It is characterized by being in the following range.

The polyarylene sulfide resin composition used in the present invention comprises a polyarylene sulfide resin (A) as an essential component. The polyarylene sulfide resin used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyarylene sulfide resin has the following general formula (1)

(Wherein R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). And, if necessary, the following general formula (2)

And a trifunctional structural moiety represented by formula (1). The trifunctional structural moiety represented by the formula (2) is preferably in the range of 0.001 mol% to 3 mol% or less, particularly 0.01 mol% or more with respect to the total number of moles with other structural moieties. To 1 mol% or less.

Here, in the structural part represented by the general formula (1), R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4) are exemplified.

Among these, in particular, the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para-position represented by the general formula (3). In terms of surface.

Further, the polyarylene sulfide resin is not limited to the structural portion represented by the general formulas (1) and (2), but the following structural formulas (5) to (8)

The structural site represented by the formula (1) and the structural site represented by the general formula (2) may be included at 30 mol% or less. In particular, in the present invention, the structural site represented by the general formulas (5) to (8) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains a structural moiety represented by the above general formulas (5) to (8), the bonding mode thereof may be either a random copolymer or a block copolymer. Good.

Further, the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less with respect to the total number of moles with other structural sites, particularly 1 It is preferable that it is below mol%.

The physical properties of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.

(Melt viscosity)
The melt viscosity of the polyarylene sulfide resin used in the present invention is not particularly limited, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 [Pa · s] to 1000 [Pa · s]. Furthermore, the range of 10 [Pa · s] to 500 [Pa · s] is more preferable because the balance between fluidity and mechanical strength is improved, and in particular, the range is 60 [Pa · s] to 200 [Pa · s]. s] The following range is particularly preferable. However, in the present invention, the melt viscosity (V6) is as follows. Polyarylene sulfide resin is flow tester manufactured by Shimadzu Corporation, CFT-500D, 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm ) / 1 (mm), and the melt viscosity is measured after holding for 6 minutes.

(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 or more and 2.00 or less. When the linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.50, more preferably in the range of 0.95 to 1.20. preferable. Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.

[Wherein SR represents shear rate (second ⁻¹ ), SS represents shear stress (dyne / cm ² ), and K represents a constant. The closer the N value is to 1, the closer the PPS is to a linear structure, and the higher the N value is, the more branched the structure is.

(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited. For example, 1) dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, and if necessary polyhalogenoaromatic compound or other copolymerization component. In addition, a polymerization method, 2) a dihalogenoaromatic compound in a polar solvent in the presence of a sulfidizing agent, and a polyhalogenoaromatic compound or other copolymerization component, if necessary, and polymerization, 3) Examples thereof include a method in which p-chlorothiophenol is self-condensed by adding other copolymerization components if necessary. Among these methods, the method 2) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 2), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound in the organic polar solvent. And a sulfidizing agent, if necessary, added with a polyhalogenoaromatic compound and reacted, and the amount of water in the reaction system is 0.02 mol to 0.5 mol with respect to 1 mol of the organic polar solvent. In the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and a method for producing a polyarylene sulfide resin by controlling to a range of Add polyhalogenoaromatic compounds or other copolymerization components if necessary, alkali metal hydrosulfides and organic acid alkali metals The organic acid alkali metal salt in the range of 0.01 mol to 0.9 mol with respect to 1 mol of the sulfur source and the water content in the reaction system are 0.02 with respect to 1 mol of the aprotic polar organic solvent. What is obtained by the method of making it react, controlling in the range below a mole (refer WO2010 / 058713 pamphlet) is especially preferable. Specific examples of the dihalogenoaromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and each of the above compounds Compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring, and polyhalogenoaromatic compounds include 1,2,3-trimethyl. Lobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6- And trihalonaphthalene. Moreover, it is desirable that the halogen atom contained in each compound is a chlorine atom or a bromine atom.

The post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited. For example, (1) after the completion of the polymerization reaction, the reaction mixture is left as it is, or an acid or a base is used. After adding the solvent, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is water, a reaction solvent (or an organic solvent having an equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone. , A method of washing once or twice with a solvent such as alcohols, and further neutralizing, washing with water, filtering and drying, or (2) after completion of the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, Ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons and other solvents (soluble in the polymerization solvent used and at least A solvent that is a poor solvent for polyarylene sulfide) as a precipitating agent to precipitate solid products such as polyarylene sulfide and inorganic salts, and filter, wash, and dry these, or (3) After the completion of the polymerization reaction, the reaction mixture (or an organic solvent having an equivalent solubility with respect to the low molecular polymer) is added to the reaction mixture and stirred, and then filtered to remove the low molecular weight polymer. A method of washing once or twice with a solvent such as acetone, methyl ethyl ketone, alcohol, etc., followed by neutralization, washing with water, filtration and drying. (4) After completion of the polymerization reaction, water is added to the reaction mixture to wash with water. Filtration, if necessary, acid treatment at the time of washing with water, acid treatment and drying, (5) after completion of the polymerization reaction, the reaction mixture is filtered, and if necessary, once or twice or more with a reaction solvent Washing Further water washing, a method of filtering and drying, and the like.

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

The polyarylene sulfide resin composition of the present invention contains the epoxy resin (B) as an essential component.

The epoxy resin used in the present invention is not particularly limited as long as the effects of the present invention are exhibited. Examples thereof include bisphenol type epoxy resins, novolac type epoxy resins, and epoxy resins having a polyarylene ether structure (α). Among them, bisphenol type epoxy resin is preferable because it has excellent adhesiveness and excellent thermal shock resistance, and particularly has excellent thermal shock resistance in the TD direction as well as thermal shock resistance when having a weld portion. Can be mentioned.

As the epoxy equivalent of the epoxy resin used in the present invention, while reducing the gas generation amount at the time of melting, and excellent adhesion, not only the thermal shock resistance, particularly the thermal shock resistance when having a weld part, From the viewpoint of excellent thermal shock resistance in the TD direction, 2400 [g / eq. ], More preferably 2100 [g / eq. ], More preferably 1900 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, it is preferably 100 [g / eq. ], More preferably 190 [g / eq. ], More preferably 210 [g / eq. ] The above range.

Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, Examples thereof include bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin. In the case of a bisphenol type epoxy resin, while reducing the amount of gas generated at the time of melting, it has excellent adhesiveness, and also has a thermal shock property, particularly a thermal shock property in the case of having a weld portion, as well as a thermal shock in the TD direction. From the viewpoint of excellent properties, it is preferably 2400 [g / eq. ], More preferably 2100 [g / eq. ], More preferably 1900 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, it is preferably 100 [g / eq. ], More preferably 190 [g / eq. ], More preferably 210 [g / eq. ] The above range.

Examples of the novolac type epoxy resin include novolac type epoxy resins obtained by reacting novolac type phenol resins obtained by condensation reaction of phenols and aldehydes with epihalohydrin. Specific examples include phenol novolacs. Type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, and brominated phenol novolak type epoxy resin. When the epoxy resin is a novolak type epoxy resin, the gas generation amount at the time of melting is reduced, and the adhesiveness is excellent. Furthermore, not only the thermal shock resistance, particularly the thermal shock resistance in the case of having a weld part, the TD direction From the viewpoint of excellent thermal shock resistance, it is preferably 300 [g / eq. ], More preferably 250 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, it is preferably 100 [g / eq. ], More preferably 190 [g / eq. ] The above range.

As the epoxy resin (B) used in the present invention, one or more of the above-mentioned various types can be used in combination.

The polyarylene sulfide resin composition of the present invention contains an epoxy group-containing polyolefin (C) as an essential component.

When the epoxy group-containing polyolefin further imparts a functional group, for example, by homopolymerization of α-olefin or copolymerization of different α-olefins, the α-olefin and the vinyl polymerizable compound having a functional group and Can be obtained by copolymerization. Examples of the α-olefin include those having 2 to 8 carbon atoms such as ethylene, propylene and butene-1. Moreover, an epoxy group (glycidyl group) is mentioned as a functional group.

Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, and the like. Examples thereof include acids, itaconic acid and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), and glycidyl (meth) acrylate. Among these, the above-mentioned ethylene-propylene copolymer and ethylene-butene copolymer having an epoxy group are preferable from the viewpoint of improving mechanical strength, particularly toughness and impact resistance.

As the epoxy group-containing polyolefin (C) used in the present invention, one or more of the above-mentioned various types can be used in combination. In the epoxy group-containing polyolefin (C) used in the present invention, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in 1 g of the polyarylene sulfide resin composition described later is a predetermined amount. It may be used while appropriately adjusting so as to be, while reducing the amount of gas generation at the time of melting, and excellent adhesiveness, in addition to the thermal shock resistance, especially when having a weld portion, From the viewpoint of excellent thermal shock resistance in the TD direction, the epoxy equivalent of the epoxy group-containing polyolefin (C) is preferably 5000 [g / eq. ], More preferably 4900 [g / eq. ], More preferably 4800 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, preferably 1200 [g / eq. ], More preferably 1300 [g / eq. ], More preferably, 1400 [g / eq. ] The above range.

In the present invention, while reducing the amount of gas generated at the time of melting, it is excellent in adhesiveness, and further, not only thermal shock resistance, particularly in the case of having a weld part, but also in thermal shock resistance in the TD direction. From an excellent viewpoint, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in 1 g of the polyarylene sulfide resin composition is in the range of 25 [μmol] or more, and adhesion and From the viewpoint of improving not only the thermal shock property, particularly the thermal shock property in the case of having a weld portion, but also the thermal shock property in the TD direction, a range of 30 [μmol] or more is preferable, and a range of 35 [μmol] or more is more preferable. In addition, from the viewpoint of reducing the amount of gas generated and excellent fluidity, the range is 300 [μmol] or less, and the range of 270 [μmol] or less is preferred. The range of 250 [μmol] or less is more preferable.

Furthermore, it is more preferable that the ratio of the epoxy group of the epoxy resin (B) in 1 g of the polyarylene sulfide resin composition is in the range of 20 [μmol] to 250 [μmol], and the epoxy group-containing polyolefin (C It is more preferable that the ratio of the epoxy group possessed by () is in the range of 5 [μmol] to 50 [μmol].

The blending ratios of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in the polyarylene sulfide resin composition of the present invention are the same as the epoxy resin (B) and the epoxy group-containing polyolefin in 1 g of the polyarylene sulfide resin composition. Especially when the epoxy resin (B) and the epoxy group-containing polyolefin (C) are blended at a blending ratio in which the total proportion of epoxy groups possessed by (C) is in the range of 25 [μmol] to 300 [μmol]. Although not limited, it is preferable that the epoxy resin (B) is in the range of 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. From the viewpoint of epoxy resin adhesiveness and thermal shock resistance, 7 A range of more than 9 parts by mass is more preferred, and a range of more than 9 parts by mass is more preferred. And from the viewpoint of thermal shock resistance and gas generation amount, it is more preferably 28 parts by mass or less, and further preferably 26 parts by mass or less. Similarly, the epoxy group-containing polyolefin (C) is preferably in the range of 5 parts by mass or more and 30 parts by mass or less, and from the viewpoint of epoxy resin adhesion, thermal shock resistance, and impact resistance, it is 7 parts by mass or more. More preferred is a range, more preferred is a range of 9 parts by mass or more, and more preferred is a range of 28 parts by mass or less from the viewpoint of the amount of gas generated. preferable. Furthermore, the epoxy resin (B) has an epoxy group amount from the viewpoint of excellent epoxy adhesiveness and thermal shock resistance, particularly not only the thermal shock resistance in the case of having a weld portion, but also excellent thermal shock resistance in the TD direction. Is preferably blended so as to be larger than the epoxy group amount of the epoxy group-containing polyolefin (C).

The polyarylene sulfide resin composition used in the present invention comprises glass fiber (D1) as an essential component.

As the glass fiber, chopped strands used for injection molding compounds are preferably used. The fiber diameter and fiber length are not particularly limited as long as the effects of the present invention are not impaired, but the fiber diameter (diameter) is preferably in the range of 3 μm to 20 μm, more preferably in the range of 6 μm to 13 μm. Although the length of the glass fiber is arbitrary, it is preferable to reduce the amount of deformation of the molded product due to the balance between the mechanical properties and deformation of the molded product, but the average fiber is preferred in terms of mechanical strength. The length is preferably at least 30 μm and longer, and is appropriately selected according to the required performance. Usually, the range of 50 μm to 2000 μm is preferable. There is no restriction on the cross-sectional shape of the glass fiber, and a round shape is usually used. A similar cross-sectional shape is preferable, and a flat cross-sectional shape is particularly preferable.

The glass fiber used in the present invention is preferably pretreated with a silane coupling agent or the like.

The blending ratio of the glass fibers is preferably in the range of 10 to 350 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin, and the viewpoint of improving heat resistance, mechanical strength, particularly thermal shock resistance. Is more preferably in the range of 20 parts by mass or more, more preferably in the range of 30 parts by mass or more, and from the viewpoint of improving dimensional stability and fluidity, it is in the range of 100 parts by mass or less. More preferably, the range is 80 parts by mass or less.

The polyarylene sulfide resin composition used in the present invention contains glass flakes (D2) as an essential component.

As the glass flakes used in the present invention, known glass flakes can be used as long as they are scale-like glass fillers. Among these, the average particle diameter is in the range of 10 μm to 4000 μm and / or the average thickness is. What is a glass flake in the range of 0.1 μm or more to 20 μm or less is preferable, and the average particle diameter is in the range of 100 μm or more to 300 μm or less and / or the average thickness from the viewpoint of excellent moisture permeability and surface appearance. Is preferably in the range of 2 μm to 10 μm. When the average particle size is 100 μm or more and / or the average thickness is 2 μm or more, it suppresses the deterioration of the surface appearance that occurs because the glass flakes float with glass fibers on the surface of the molded product On the other hand, even when an average particle size of 300 μm or less and / or an average thickness of 10 μm or less is used, part of the glass flakes is crushed during melt kneading, As a result of being easily formed, the phenomenon of floating on the surface of the molded article with glass fibers and impairing the surface appearance is preferable.

In the present invention, the average particle size and the average thickness mean a particle size of 50% cumulative degree obtained from a cumulative particle size distribution curve measured by a laser light diffraction method.

The glass flakes used in the present invention are preferably pretreated with a silane coupling agent or the like.

In the present invention, by using such scaly glass flakes to be dispersed in a molded product, the linear expansion coefficient in the flow direction and the right-angle direction can be reduced, and the thermal shock resistance of repeating low and high temperatures can be improved. .

The blending ratio of the glass flakes is not only the adhesiveness, heat resistance, mechanical strength, thermal shock resistance, particularly the thermal shock resistance in the case of having a weld part, but also cooling in the TD direction with respect to 100 parts by mass of the polyarylene sulfide resin. From the viewpoint of excellent impact properties and from the viewpoint of improving dimensional stability, it is preferably in the range of 1 part by mass or more, more preferably in the range of 20 parts by mass or more, and in the range of 30 parts by mass or more. More preferably. On the other hand, from the viewpoint of improving mechanical strength and moldability, a range of 250 parts by mass or less is preferable, a range of 100 parts by mass or less is more preferable, and a range of 80 parts by mass or less is more preferable.

The blending ratio of the glass fiber and the glass flake is not particularly limited as long as the effect of the present invention is achieved, but it is preferable that the blending ratio of the glass fiber is larger than the glass flake from the viewpoint of improving the mechanical strength, From the viewpoint of improving the dimensional stability, it is preferable that the blending ratio of the glass flake is larger than that of the glass fiber.

The polyarylene sulfide resin composition used in the present invention is a filler other than the glass fibers (D1) and the glass flakes (D2) as necessary, as long as the effects of the present invention are not impaired. (Referred to as “agent”) as an optional component. As these other fillers, known and conventional materials can be used as long as they do not impair the effects of the present invention. For example, various fillers such as fibrous ones and non-fibrous ones such as granular or plate-like ones can be used. Examples of the filler are shapes. Specifically, fibrous fillers such as carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers can be used. Also non-fibrous such as glass beads, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber, calcium sulfate Fillers can also be used.

In the present invention, other fillers are not essential components, and when added, the content is not particularly limited as long as the effects of the present invention are not impaired. The content of the other filler is, for example, preferably 1 part by mass or more, more preferably 10 parts by mass or more, preferably 600 parts by mass, more preferably 100 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A). The range is 200 parts by mass or less. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

The polyarylene sulfide resin composition used in the present invention can contain a silane coupling agent as an optional component, if necessary, within the range where the effects of the present invention are exhibited. The silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but a silane coupling agent having a functional group that reacts with a carboxy group, for example, an epoxy group, an isocyanato group, an amino group, or a hydroxyl group is preferable. Can be mentioned. Examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compounds, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. It is done. These alkoxysilane compounds are preferred because they can react with the polyarylene sulfide polymer via a functional group to give an apparent molecular weight. In the present invention, the silane coupling agent is not an essential component, but when it is added, the amount added is not particularly limited as long as the effects of the present invention are not impaired, but the polyarylene sulfide resin (A) is 100 parts by mass. Is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Within such a range, the resin composition is preferable because it has good corona resistance and moldability, in particular, releasability, and the molded product exhibits excellent adhesiveness with the epoxy resin and further improves the mechanical strength.

The polyarylene sulfide resin composition used in the present invention can contain a thermoplastic elastomer other than the epoxy group-containing polyolefin (C) as an optional component, as necessary, within the range where the effects of the present invention are exhibited. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among these, polyolefin-based elastomers are preferable. When these elastomers are added, the content is not particularly limited as long as the effects of the present invention are not impaired, but with respect to 100 parts by mass of the polyarylene sulfide resin (A), preferably 0.01 parts by mass or more. The range is preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Within such a range, the resulting polyarylene sulfide resin composition is preferred because the impact resistance is improved.

The polyolefin-based elastomer is obtained by, for example, homopolymerization of α-olefin or copolymerization of different α-olefins with a functionalized vinyl polymerizable compound in the case of further adding a functional group. It can be obtained by copolymerization. Examples of the α-olefin include those having 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group is not particularly limited as long as it is a functional group other than an epoxy group, and examples thereof include carboxy groups, acid anhydride groups represented by the formula — (CO) O (CO) —, those Ester, amino group, hydroxyl group, mercapto group, isocyanate group, or oxazoline group.

Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, and the like. Examples thereof include acids, itaconic acid and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), and glycidyl (meth) acrylate. Among these, an ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the above-described epoxy group, carboxy group, and acid anhydride group are mechanically selected. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.

Furthermore, the polyarylene sulfide resin composition used in the present invention can contain a resin other than the epoxy resin (B) and the epoxy group-containing polyolefin (C) as an optional component within a range not impairing the effects of the present invention. Such resins include polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyether ketone resins, polyarylenes. Resin, polyethylene resin (excluding epoxy group-containing polyolefin (C)), polypropylene resin (excluding epoxy group-containing polyolefin (C)), polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, Synthetic resins such as urethane resins and liquid crystal polymers can be contained as optional components. In addition, the content of these resins varies depending on the purpose and cannot be specified unconditionally, but from 0.01 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In the following range, it may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention.

In addition, the polyarylene sulfide resin composition used in the present invention is a colorant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, foaming, as long as the effects of the present invention are not impaired. You may contain well-known and usual additives, such as an agent, a flame retardant, a flame retardant adjuvant, a rust preventive agent, and a mold release agent, as an arbitrary component as needed. These additives are not essential components. For example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), the effect of the present invention is not impaired, preferably in the range of 0.01 parts by mass to 1000 parts by mass. It may be used by appropriately adjusting according to the purpose and application.

Examples of other mold release agents include natural waxes such as carnauba wax, metal salts of higher fatty acids such as zinc stearate, and polyolefin waxes such as oxidized or non-oxidized polyethylene wax.

The epoxy resin or epoxy group-containing polyolefin used in the present invention is melt kneaded in the presence of a component acting as a so-called curing agent (hereinafter referred to as a curing agent acting component) such as a phenol resin, an amine (active hydrogen compound), or a carboxylic acid anhydride. Sometimes the epoxy group disappears due to curing reaction (addition reaction with active hydrogen compound, copolycondensation reaction with acid anhydride), so the proportion of curing agent active component in polyarylene sulfide resin composition is in the epoxy resin component The active group in the curing agent working component is 0.1 equivalent or less, more preferably 0.01 equivalent or less, and most preferably 0 equivalent, that is, absent (less than the detection limit amount) with respect to 1 epoxy group in total. It is.

The polyarylene sulfide resin composition used in the present invention comprises polyarylene sulfide resin (A), epoxy resin (B), epoxy group-containing polyolefin (C), glass fiber (D1), and glass flake (D2) as essential components. The polyarylene sulfide resin (A) is obtained by a production method including a step of melt-kneading at a melting point or higher.

A preferred method for producing the polyarylene sulfide resin composition used in the present invention is that the polyarylene sulfide resin (A), the epoxy resin (B), the epoxy group-containing polyolefin (C) and the glass flakes ( Each component of D2) and optional components such as other fillers and additives as described above can be used in various forms such as powders, pellets, strips, etc. for ribbon blenders, Henschel mixers, V blenders, etc. After being charged and dry blended, it is charged into a known melt kneader such as a Banbury mixer, a mixing roll, a single or twin screw extruder and a kneader, and the glass fiber (D1) is extruded from the side feeder of the melt extruder. It is preferable to put in the machine from the viewpoint of suppressing dispersibility and fiber breakage. Further, the resin temperature in the extruder is not less than the melting point of the polyarylene sulfide resin, preferably not less than the melting point + 10 ° C., more preferably not less than the melting point + 10 ° C., more preferably not less than the melting point + 20 ° C., preferably not more than the melting point + 100 ° C., more preferably It can be manufactured through a step of melt kneading in a temperature range of melting point + 50 ° C. or less. Addition and mixing of each component to the melt kneader may be performed simultaneously or may be performed separately.

The melt kneader is preferably a biaxial kneader / extruder from the viewpoints of dispersibility and productivity. For example, a resin component discharge rate ranging from 5 (kg / hr) to 500 (kg / hr) or less, a screw It is preferable to melt-knead while adjusting the rotation speed from 50 (rpm) to 500 (rpm) as appropriate, and the ratio (discharge amount / screw rotation speed) is 0.02 (kg / hr / rpm). ) From the above, it is more preferable to melt-knead under conditions that are in the range of 5 (kg / hr / rpm) or less. The position of the side feeder is such that the ratio of the distance from the extruder resin charging part to the side feeder with respect to the total screw length of the biaxial kneading extruder is preferably 0.1 or more, more preferably 0.3 or more. Therefore, the range is preferably 0.9 or less, more preferably 0.7 or less.

Thus, the polyarylene sulfide resin composition used in the present invention obtained by melt-kneading is composed of the essential components polyarylene sulfide resin (A), epoxy resin (B), epoxy group-containing polyolefin (C) and glass fiber ( D1), glass flakes (D2), and a molten mixture containing optional components to be added as necessary and components derived from them, and after the melt-kneading, they are processed into pellets, chips, granules, powders and the like by known methods Then, it is preferable to perform preliminary drying at a temperature of 100 ° C. or higher and 150 ° C. or lower as necessary to provide various types of molding.

The polyarylene sulfide resin composition used in the present invention produced by the above production method has a polyarylene sulfide resin as a matrix, and the epoxy resin (B) and the epoxy group-containing polyolefin (C) as essential components in the matrix. A glass fiber (D1), glass flake (D2), a component derived therefrom, and a morphology in which an optional component added as necessary is dispersed are formed. As a result, the polyarylene sulfide resin molded article can have excellent epoxy resin adhesion, heat resistance, mechanical strength, thermal shock resistance, and dimensional stability.

The molded article of the present invention can be obtained by melt-molding the polyarylene sulfide resin composition. As a melt molding, a general method may be used, which can be used for various moldings such as injection molding, insert molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, In particular, it is excellent in releasability, so it is suitable for injection molding applications. In the case of molding by injection molding or insert molding, various molding conditions are not particularly limited, and can be usually molded by a general method. For example, in an injection molding machine, the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably the melting point + 10 ° C. or higher, more preferably the melting point + 10 ° C. or higher, more preferably the melting point + 20 ° C. or higher, preferably the melting point + 100 ° C. or lower. More preferably, after the step of melting the polyarylene sulfide resin composition in the temperature range of the melting point + 50 ° C. or lower, the resin discharge port may be injected into the mold and molded. At that time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) or higher, preferably 120 ° C. or higher, preferably 300 ° C. or lower, more preferably 180 ° C. or lower.

The polyarylene sulfide resin molded product used in the present invention is excellent in adhesiveness, that is, adhesiveness with a curable resin composition containing an epoxy resin. Here, the curable resin composition containing an epoxy resin is preferably a composition obtained by mixing an epoxy resin and a curing agent.

The epoxy resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bisphenol type epoxy resins, novolac type epoxy resins, and epoxy resins having a polyarylene ether structure (α). Of these, bisphenol-type epoxy resins are preferred because of their excellent adhesiveness.

Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, Examples thereof include bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin.

Examples of the novolac type epoxy resin include novolac type epoxy resins obtained by reacting novolac type phenol resins obtained by condensation reaction of phenols and aldehydes with epihalohydrin. Specific examples include phenol novolacs. Type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, and brominated phenol novolak type epoxy resin.

These epoxy resins contained in the curable resin composition used in the present invention are preferably used after being cured with a curing agent. The curing agent is not particularly limited as long as it is generally used as a curing agent for epoxy resins. For example, an amine type curing agent, a phenol resin type curing agent, an acid anhydride type curing agent, and a latent property. Examples thereof include a curing agent.

As the amine type curing agent, known ones can be used, and aliphatic polyamines, aromatic polyamines, heterocyclic polyamines, their epoxy adducts, Mannich modified products, and polyamide modified products can be used. Specifically, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis ( 4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di- Examples thereof include p-aminobenzoate. Of these, m-xylenediamine and 1,3-bisaminomethylcyclohexane are particularly preferred because of their excellent curability.

As the phenol resin type curing agent, known ones can be used, for example, bisphenols such as bisphenol A, bisphenol F, and biphenol, tri (hydroxyphenyl) methane, 1,1,1-tri (hydroxyphenyl) ethane. And trifunctional phenolic compounds such as phenol novolac, cresol novolac and the like.

As the acid anhydride type curing agent, known ones can be used. For example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, anhydrous Examples thereof include methyl nadic acid, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

Examples of latent curing agents include dicyandiamide, imidazole, BF3-amine complex, and guanidine derivatives.

These curing agents can be used alone or in combination of two or more. In addition, a curing accelerator can be used in appropriate combination as long as the effects of the present invention are not impaired. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.

The curable resin composition containing an epoxy resin used in the present invention may be allowed to undergo a curing reaction in the absence of a solvent, but benzene, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile Curing reaction in a solvent such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyrrolidone, isopropyl alcohol, isobutanol, and t-butyl alcohol May be.

In the curable resin composition used in the present invention, the use ratio of the epoxy resin and the curing agent is not particularly limited as long as it is a known ratio within a range not impairing the effect of the present invention, but is excellent in curability. Since a cured product having excellent heat resistance and chemical resistance of the cured product is obtained, the active group in the curing agent is from 0.7 equivalent to 1. An amount in the range of 5 equivalents or less is preferred.

Since the molded product formed by molding the polyarylene sulfide resin composition used in the present invention is excellent in epoxy resin adhesion, it is a composite molded product formed by bonding with a cured product of a curable resin composition containing an epoxy resin. It can be used suitably.

The composite molded article of the present invention can be produced by a method including a step of adhering a molded article formed by melt molding a polyarylene sulfide resin composition and a cured product of a curable resin composition containing an epoxy resin. .

The adhesive between the molded product and the cured product may be a known method as long as the effects of the present invention are not impaired. However, the molded product is brought into contact with a curable resin composition containing an epoxy resin, and the curable resin is contacted. A method including a step of curing the composition may be mentioned. Further, at least a part of the surface to be bonded to the curable resin composition at the time of bonding, preferably 50% or more, more preferably the entire surface is heated and melted, and then a curable resin containing an epoxy resin. The method of making a composition contact and hardening this curable resin composition is also mentioned. On the other hand, the curable resin composition is cured by bringing the curable resin composition in an uncured state into contact with the molded article and then completely curing the curable resin composition, After being in a cured state (so-called B-stage state), it can be completely cured by contacting with the molded product.

The composite molded product of the present invention thus obtained can be used for various applications. Examples of main applications include housings for electronic devices such as various home appliances, mobile phones, and PCs (Personal Computers), protection / support members for box-type electrical / electronic component integrated modules, multiple individual semiconductors or modules, Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, Small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts and other electrical and electronic parts; VTR parts, TV parts, irons , Hair dryer, rice cooker parts , Microwave oven parts, audio parts, audio / video equipment parts such as audio / laser disc / compact disc / DVD disc / Blu-ray disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, water heater and bath Household appliances, office electrical product parts, such as water heater parts, temperature sensors, etc .; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, Machine-related parts typified by writers and typewriters: Optical equipment typified by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, brush holders, slip rings, IC regulators, for light dimmers Potentiometer Various valves such as base, relay block, inhibitor switch, exhaust gas valve, fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust Gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor , Water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, ignition And its bobbins, motor insulators, motor rotors, motor cores, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, connectors for fuses, horn terminals, electrical component insulation plates, Step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, power module, inverter, power device, intelligent power module, insulated gate bipolar transistor, power control unit, reactor, Converter, capacitor, insulator, motor terminal block, battery, electric compressor, battery The present invention is also applicable to automobile / vehicle-related parts such as a case that houses a terry current sensor, a junction block, an ignition coil for a DLI system, and other various uses.

Hereinafter, the present invention will be described in more detail with specific examples. Parts and% are based on mass unless otherwise specified. Moreover, the analysis of resin manufactured in the manufacture example was performed on the following conditions, respectively.

(Examples 1 to 8 and Comparative Examples 1 to 6) Production of PPS resin compositions According to the composition components and blending amounts shown in Tables 1 and 2, the materials were uniformly mixed with a tumbler. Thereafter, the blended material was put into a twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd., and the resin component discharge rate was 25 kg / hr, the screw rotation speed was 200 rpm, and the resin component discharge rate (kg / hr). The ratio of the screw rotation speed (rpm) (discharge amount / screw rotation speed) = 0.1 (kg / hr · rpm) and melt kneading at a set resin temperature of 320 ° C. to obtain resin composition pellets. The following adhesion test was performed using this pellet. The results of the test and evaluation are shown in Tables 1 to 4.

(Measurement example) Adhesive strength between PPS molded product and epoxy resin (epoxy adhesive strength)
Next, the obtained pellets were supplied to an injection molding machine (SE75D-HP) manufactured by Sumitomo Heavy Industries set at a cylinder temperature of 310 ° C., and injected using an ASTM No. 1 dumbbell mold for molding at a mold temperature of 140 ° C. Molding was performed to obtain ASTM No. 1 dumbbell pieces. Then, ASTM No. 1 dumbbell piece is divided into two equal parts from the center and masked with fluororesin adhesive tape (Teflon (registered trademark) tape) (thickness: 0.08 mm) so that the contact area with the epoxy adhesive is 170 mm ^2. Then, an epoxy resin (two-pack type epoxy resin manufactured by Nagase ChemteX Corporation, main component: XNR5002, curing agent: XNH5002, mixing ratio is main agent: curing agent = 100: 90) was applied (application area: 12.9 mm × 12.9 mm). The other side was bonded to the coated surface, fixed using a clip, and heated and cured / adhered in a hot air dryer set at 135 ° C. for 3 hours. After cooling at 23 ° C. for 1 day, the spacer was removed, and the obtained test piece was obtained. Then, the strain rate was 5 mm / min, the distance between the fulcrums was 60 mm, and the tensile strength at break using an Instron tensile tester at 23 ° C. And the value divided by the adhesion area was defined as the epoxy adhesive strength (MPa).

(Measurement Method) Cold and Thermal Shock Resistance (Heat Cycle) Test of Molded Product Having Weld Part Evaluation of cold and thermal shock resistance was performed using a molded product having a weld part shown below. In addition, the said evaluation was implemented by using the molded article which insert-molded the metal member with a large thermal expansion coefficient in order to set it as an acceleration test.

A steel insert block member having a length of 25 mm, a width of 40 mm, and a thickness of 10 mm connects the midpoints of the sides in the vertical direction of the member, and has a thickness of 3.55 mm on a straight line parallel to the side in the horizontal direction of the member. Preparing an insert block member having a diameter center of two through-holes parallel to the vertical direction, the diameter centers of the through-holes being arranged 20 mm apart from each other about the midpoint of the straight line; The insert block member is held inside the injection mold by using the two through holes and two steel cylindrical pins installed in the injection mold. After the installation and injection molding of the pellets of the polyphenylene sulfide resin composition, the entire outer periphery of the insert block member is coated with a polyphenylene sulfide resin composition having a thickness of 1 mm, and we Using an injection molding die which is designed to part d is formed to obtain the polyphenylene sulfide resin composition pellets were injection-molded moldings. Using the obtained molded product of the polyphenylene sulfide resin composition encapsulating the insert block member, in the gas phase type thermal shock tester, the temperature is maintained at −40 ° C./1 hour to 140 ° C./1 hour. The thermal shock test which makes a cycle was implemented, and the number of cycles until a crack generate | occur | produces and it fractures was measured.

(Measuring method) Cold and thermal shock resistance (heat cycle property) test in the TD direction of the molded product (without the weld portion) Evaluation of the thermal and thermal shock resistance in the TD direction was performed using the molded product (without the weld portion) shown below. . In order to make the evaluation an accelerated test, a metal member having a large thermal expansion coefficient (FIG. 1) is insert-molded so that the four corners of the metal member are not covered with the resin member so that cracks in the TD direction occur. It implemented by using the molded article (FIG. 2) which provided the non-coating part (L).
First, a steel insert block member (M) shown in FIG. 1 having a length of 56 mm, a width of 66 mm, and a thickness of 5 mm is prepared, and then four through holes (h) provided at the corners of the member and injection are prepared. Using four steel cylindrical pins installed inside the molding die, the insert block member (M) is installed so as to be held inside the injection molding die and melted. The polyphenylene sulfide resin composition flows from the side F ₁ side to the F ₂ side, and a gate portion and a liquid escape portion are formed so that a weld portion is not formed. After injection molding, on the insert block member (M) Using an injection mold designed so that the lower surface is coated with a resin part having a thickness of 1 mm as shown in FIG. 2, pellets of the polyphenylene sulfide resin composition are injection molded to obtain a molded product (P). The

A thermal shock test was conducted in a gas-phase type thermal shock tester with a temperature cycle of −40 ° C./1 hour to 170 ° C./1 hour held as one cycle of the thermal cycle. It was measured.

(Measurement method) Gas generation amount (weight reduction rate during heating)
Using a Rigaku differential thermal balance TG8120, 10 g of the resin composition pellets obtained by melt-kneading were weighed, heated from 50 ° C. to 325 ° C. at 20 ° C./min, and then heated at 325 ° C. for 3 hours. The weight loss rate before and after heating was measured.
This weight reduction rate corresponds to the amount of gas generated from the pellets during heating. Since this gas generation amount is more excellent in view of mold maintenance, surface appearance, mechanical properties and moldability, it was classified according to the following evaluation criteria in practical use.

◎ (very good): 2.0% or less range ○ (good): 2.0% to 2.2% range △ (sufficient): 2.2% to 2.5% range × (Insufficient): Over 2.5% range

In Tables 1 to 4, the compounding ratios of the blended resin and material represent parts by mass, and the followings were used.

Polyphenylene sulfide resin (A-1) The one produced by the following (Production Example 1) was used.

(Production Example 1) Production of polyphenylene sulfide resin (a-1) [Step 1]
In a 150 liter autoclave with a stirring blade connected to a pressure gauge, thermometer, condenser, decanter, and rectifying column, 33.222 kg (226 mol) of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”), NMP3. 420 kg (34.5 mol), 47.33% by weight NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 wt% NaOH aqueous solution 18.533 g (228 mol as NaOH) were charged and stirred under a nitrogen atmosphere Then, the temperature was raised to 173 ° C. over 5 hours to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB distilled azeotropically during dehydration was separated with a decanter and returned to the autoclave as needed. After completion of the dehydration, the finely divided anhydrous sodium sulfide composition was dispersed in p-DCB in the autoclave. Since the NMP content in this composition was 0.079 kg (0.8 mol), 98 mol% (33.7 mol) of the charged NMP was an NMP ring-opened product (4- (methylamino)). It was shown to be hydrolyzed to the sodium salt of butyric acid (hereinafter abbreviated as “SMAB”). The amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave. When the total amount of NaSH and NaOH charged is changed to anhydrous Na ₂ S, the theoretical dehydration amount is 27.921 g, so 609 g (33.8 mol) of the remaining water amount in the autoclave is 878 g (48.8 mol). Is consumed in the hydrolysis reaction of NMP and NaOH and does not exist in the autoclave as water, and the remaining 269 g (14.9 mol) remains in the autoclave in the form of water or crystal water. Was showing. The amount of water in the autoclave was 0.065 mol per mol of sulfur atoms present in the autoclave.

[Step 2]
After the dehydration step, the internal temperature was cooled to 160 ° C., NMP46.343 kg (467.5 mol) was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave. The amount of distilled water was 228 g (12.7 mol).

[Step 3]
The water content in the autoclave at the start of Step 3 was 41 g (2.3 mol), 0.005 mol per mol of NMP charged in Step 2, and 0.010 mol per mol of sulfur atoms present in the autoclave. . The amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave, as in Step 1. Next, the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, then heated to 250 ° C. and stirred for 1 hour. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.40 MPa. After cooling, 650 g of the obtained slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated 4 times. The cake was again adjusted to pH 4.0 by adding 3 liters of warm water and acetic acid, stirred for 1 hour, washed, and then filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated twice. Drying at 120 ° C. overnight using a hot air drier gave white powdery PPS resin (A-1). The melt viscosity of this polymer at 300 ° C. was 41 Pa · s. The non-Newton index was 1.07.

(A-2) The product produced in the following (Production Example 2) was used.
(Production Example 2)
“Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, then heated to 250 ° C. and stirred for 1 hour.” The temperature was raised from 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1.5 hours, then heated to 250 ° C. and stirred for 1 hour. ” A white powdery PPS resin (hereinafter referred to as A-2) was obtained. The resulting polymer had a melt viscosity of 73 Pa · s and a non-Newtonian index of 1.07.

(A-3) The one produced in the following (Production Example 3) was used.

(Production Example 3)
A 150-liter autoclave with a pressure gauge, a thermometer, a condenser connected to a stirring blade and a bottom valve was charged with flaky sodium sulfide (60.3% by weight Na ₂ S) (19.413 kg) and NMP (45.0 kg). While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 4.644 kg of water (the amount of water remaining was 1.13 mol per mol of sodium sulfide). The autoclave was then sealed and cooled to 180 ° C., and charged with 22.185 kg of paradichlorobenzene, 0.027 kg of 1,2,4-trichlorobenzene and 18.0 kg of NMP. The temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After maintaining at a liquid temperature of 240 ° C. for 2 hours, the reaction was allowed to proceed with stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was sprinkled to cool. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 0.85 MPa. After the reaction, the mixture was cooled, and at a temperature of 170 ° C., a solution containing 0.284 kg (2.25 mol) of oxalic acid dihydrate in 0.663 kg of NMP was injected under pressure. After stirring for 30 minutes, the mixture was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter flat plate filter and pressure filtered at 120 ° C., and 16 kg of NMP was added, followed by pressure filtration. After filtration, the mixture was stirred for 2 hours at 150 ° C. under reduced pressure using a 150 liter vacuum dryer equipped with a stirring blade to remove NMP to obtain a white powdery PPS resin (A-3). The melt viscosity of this polymer at 300 ° C. was 77 Pa · s. The non-Newton index was 1.25.

Epoxy resin (b-1): Bisphenol A type epoxy resin “Epiclon 7050” manufactured by DIC Corporation (epoxy equivalent 1900 [g / eq.]) In the present invention, the epoxy equivalent of the epoxy resin conforms to JIS K7236 (2001). This is the value measured.
(B-2): Cresol novolac-type epoxy resin “Epiclon N-695P” (epoxy equivalent 210 [g / eq.]) Manufactured by DIC Corporation
(B-3): Bisphenol A type epoxy resin “Epiclon HM-101” manufactured by DIC Corporation (epoxy equivalent 3900 [g / eq.])
(B-4): Bisphenol A type epoxy resin “Epicoat 1009” manufactured by Japan Epoxy Resin Co., Ltd. (epoxy equivalent 2900 [g / eq.])

Polyolefin resin (c-1): ethylene / methyl acrylate / glycidyl methacrylate (67/27/6 mass%) copolymer “Bond First 7M” (epoxy equivalent 2369 [g / eq.]) Manufactured by Sumitomo Chemical Co., Ltd. In the present invention, the epoxy equivalent of the polyolefin resin is a calculated value based on each component in the raw material and its ratio. In addition, each component in the raw material and its ratio can be confirmed from delivery specifications, catalogs, etc.
(C-2): ethylene / methyl acrylate / glycidyl methacrylate (70/27/3 mass%) copolymer “Bond First 7L” (epoxy equivalent 4738 [g / eq.]) Manufactured by Sumitomo Chemical Co., Ltd.
(C-3): ethylene / glycidyl methacrylate (88/12% by mass) copolymer “Bond First E” (epoxy equivalent 1185 [g / eq.]) Manufactured by Sumitomo Chemical Co., Ltd.
(C-4): Ethylene-1-octene copolymer “engage 8842” manufactured by Dow Chemical Co., Ltd.
(C-5): Ethylene / maleic anhydride / ethyl acrylate copolymer “Bondaine AX8390” manufactured by Sumitomo Chemical Co., Ltd.
(C-6): Polyester elastomer “Perprene P150B” manufactured by Toyobo Co., Ltd. (a copolymer comprising an aromatic polyester and an aliphatic polyether)

Inorganic filler (d-1): Glass fiber (glass fiber chopped strand having a fiber diameter of 10 μm and a length of 3 mm)
(D-2): Glass flakes (“REFG-301” manufactured by Nippon Sheet Glass Co., Ltd., average thickness 5 μm, average particle size 160 [μm])

Other (e-1): Calcium montanate (“CaV-102” manufactured by Clariant Japan Co., Ltd.)
(E-2): Ethylenediamine / stearic acid / sebacic acid polycondensate “Right Amide WH-255” manufactured by Kyoeisha Chemical Co., Ltd.

h: Through hole M ... Insert block member P ... Molded product L ... Uncoated part F ₁ ... Flow direction of molten resin (gate part side)
F ₂ ... Flow direction of molten resin (liquid escape part side)

Claims (9)

1. A polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1) and glass flakes (D2),
   With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber (D1) is in the range of 10 parts by mass to 350 parts by mass, and the glass flake (D2) is 1 part by mass to 250 parts by mass. Range,
   In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [μmol] to 300 [μmol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. ] A polyarylene sulfide resin composition characterized by being in the following range.
2. In 1 g of the polyarylene sulfide resin composition, the epoxy group ratio of the epoxy resin (B) is in the range of 20 [μmol] to 250 [μmol], and the epoxy group-containing polyolefin (C) has an epoxy group content. The polyarylene sulfide resin composition according to claim 1, wherein the ratio is in the range of 5 [μmol] to 50 [μmol].
3. The epoxy equivalent of the epoxy group-containing polyolefin (C) is 1200 [g / eq. ] From 5000 [g / eq. The polyarylene sulfide resin composition according to claim 1, which has the following range.
4. The polyarylene sulfide resin composition according to claim 1, which is a melt-kneaded product.
5. A molded product obtained by melt-molding the polyarylene sulfide resin composition according to any one of claims 1 to 4.
6. A composite molded product obtained by bonding the molded product according to claim 5 and a cured product of a curable resin composition containing an epoxy resin.
7. A method for producing a polyarylene sulfide resin composition comprising melt-kneading a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2). ,
   With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber (D1) is in the range of 10 parts by mass to 350 parts by mass, and the glass flake (D2) is 1 part by mass to 250 parts by mass. Range,
   In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [μmol] to 300 [μmol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. ] The manufacturing method of the polyarylene sulfide resin composition characterized by being in the following range.
8. A method for producing a composite molded article, wherein the molded article according to claim 5 is bonded to a cured product of a curable resin composition containing an epoxy resin.
9. A method for producing a composite molded article comprising a step of bringing the curable resin composition containing an epoxy resin into contact with the molded article according to claim 5 and then curing the curable resin composition.

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