WO2018056240A1

WO2018056240A1 - Polyarylene sulfide resin composition, molded article, and production method

Info

Publication number: WO2018056240A1
Application number: PCT/JP2017/033640
Authority: WO
Inventors: 洋平山口
Original assignee: Dic株式会社
Priority date: 2016-09-21
Filing date: 2017-09-19
Publication date: 2018-03-29
Also published as: JPWO2018056240A1; JP6753470B2

Abstract

Provided are a polyarylene sulfide resin composition that yields molded articles having exceptional toughness and adhesiveness with respect to epoxy resins, and molded articles of the polyarylene sulfide resin composition. Also provided are composite molded articles obtained by bonding these molded articles and a cured product of an epoxy resin. More specifically, provided are: a polyarylene sulfide resin composition containing as essential components a polyarylene sulfide resin (A), a fatty acid ester (B) that is within the range of 0.01-5 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkaline earth metal salts, the fatty acid metal salts (C) being within a range of 0.01-5 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A); molded articles; composite molded articles with an epoxy resin cured product; and methods for producing these.

Description

Polyarylene sulfide resin composition, molded article and production method

The present invention relates to a polyarylene sulfide resin composition, a molded article, and a method for producing them.

Polyarylene sulfide (hereinafter abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter also abbreviated as PPS) resin, has excellent heat resistance and mechanical strength, chemical resistance, and molding processing. It is also excellent in performance and dimensional stability. Utilizing these characteristics, it is used as electrical / electronic equipment parts, automobile parts materials and the like.

In many cases, these parts are bonded to a part material made of epoxy resin or the like as a secondary process. However, polyarylene sulfide resins have relatively poor adhesion to other resins, particularly adhesion to epoxy resins. Therefore, for example, when bonding polyarylene sulfides with epoxy adhesives, bonding polyarylene sulfide resins with other materials, or sealing electrical and electronic parts with epoxy resins, polyarylene sulfide resins and epoxy resins Inadequate adhesion with a curable resin composition containing the following (hereinafter sometimes referred to as epoxy resin adhesion) has been a problem.

Therefore, in order to improve the deterioration of the epoxy resin adhesion, an oxidized polyethylene wax is added as a release agent to the polyarylene sulfide resin composition containing the polyarylene sulfide resin and the filler, and the epoxy resin adhesion of the molded product is increased. A method for improving the balance between releasability and mechanical properties has also been proposed (see Patent Document 1). However, in this case as well, the epoxy resin adhesion of the polyarylene sulfide resin molded product was low, and it was a level that was hardly practically sufficient.

Furthermore, for the purpose of improving mold release properties, a resin composition in which an amorphous α-olefin copolymer and a fatty acid metal salt are blended with a polyphenylene sulfide-based resin composition has been studied (see Patent Document 2). . However, even in this case, it could not be said that sufficient epoxy resin adhesion was obtained.

Also obtained by molding a polyarylene sulfide resin composition containing a polyarylene sulfide resin and an olefin wax having an acid value in the range of 65 to 150 mgKOH / g and having a carboxy group and a carboxylic anhydride group. It is known that the molded article is further excellent in epoxy resin adhesion while maintaining the mechanical properties inherent in the polyarylene sulfide resin molded article (see Patent Document 3). However, even in this case, it cannot be said that sufficient adhesion with an epoxy resin is obtained, and there is room for further improvement. Furthermore, the molded product has room for improvement in toughness, particularly bending elongation strength in the TD direction (perpendicular to the resin flow direction), and particularly when the molded product is to be thinned, There was a tendency for brittle fracture to occur. For this reason, improvement of the bending elongation strength especially in TD direction was also desired.

JP 2002-012762 A JP 2004-35635 A International Publication No. 2013/141364

The problem to be solved by the present invention is to provide a polyarylene sulfide resin composition that is a molded article excellent in epoxy resin adhesion and a molded article excellent in epoxy resin adhesion obtained by molding it. It is another object of the present invention to provide a composite molded article obtained by bonding the molded article and a cured product of a curable resin composition containing an epoxy resin, and to provide a method for producing them.

Furthermore, the problem to be solved by the present invention is not only excellent in epoxy resin adhesion but also obtained by molding a polyarylene sulfide resin composition that is a molded product having excellent bending elongation strength in the TD direction. To provide a molded product excellent in epoxy resin adhesion and bending elongation strength in the TD direction, and further, composite molding formed by bonding the molded product and a cured product of a curable resin composition containing an epoxy resin It is to provide a product and a method for manufacturing them.

As a result of diligent research to solve the above-mentioned problems, the present inventor blended polyarylene sulfide resin with one or more fatty acid metal salts selected from the group consisting of fatty acid esters and fatty acid alkali metal salts and fatty acid alkali metal earth salts. As a result, the present inventors have found that the epoxy resin adhesion is excellent, and that the bending elongation strength in the TD direction is also improved, and the present invention has been completed.

That is, the present invention comprises a polyarylene sulfide resin (A), a fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts. Containing as an essential component,
The fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is related with the polyarylene sulfide resin composition characterized by being a range.

In addition, the present invention relates to a molded article formed by molding the polyarylene sulfide resin composition.

Furthermore, the present invention relates to a composite molded product obtained by bonding a molded product obtained by molding the polyarylene sulfide resin composition and a cured product of a curable resin composition containing an epoxy resin.

The present invention also includes a polyarylene sulfide resin (A), a fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts. It is related with the manufacturing method of the polyarylene sulfide resin composition characterized by melt-kneading as an essential component above the melting | fusing point of a polyarylene sulfide resin (A).

According to the present invention, a polyarylene sulfide resin composition that is a molded article excellent in epoxy resin adhesion, and a molded article excellent in epoxy resin adhesion obtained by molding the same are provided. And a cured product of a curable resin composition containing an epoxy resin can be provided, and a production method thereof can be provided.

Furthermore, according to the present invention, a polyarylene sulfide resin composition that is a molded product having not only excellent epoxy resin adhesion but also excellent bending elongation strength in the TD direction, and an epoxy resin obtained by molding the same. Providing a molded article excellent in adhesiveness and bending elongation strength in the TD direction, and further providing a composite molded article formed by bonding the molded article and a cured product of a curable resin composition containing an epoxy resin. And methods of manufacturing them.

The polyarylene sulfide resin composition of the present invention comprises at least one fatty acid metal salt selected from the group consisting of a polyarylene sulfide resin (A), a fatty acid ester (B), a fatty acid alkali metal salt and a fatty acid alkali metal earth salt. Containing (C) as an essential component,
The fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is a range.

The polyarylene sulfide resin composition of the present invention contains 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 to 3 mol%, particularly in the range of 0.01 to 1 mol%, based on the total number of moles with other structural moieties. It is preferable that

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 polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa · s], and has a good balance between fluidity and mechanical strength. Therefore, the range of 10 to 500 [Pa · s] is more preferable, and the range of 60 to 200 [Pa · s] 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 = 10/1 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 effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When the linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20. 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 are added to and reacted with a polyhalogenoaromatic compound as necessary, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by controlling (see Japanese Patent Application Laid-Open No. 07-228699), and if necessary, a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. Polyhalogenoaromatic compound or other copolymerization component is added, and alkali metal hydrosulfide and organic acid alkali metal salt are added to sulfur source 1 While controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 moles of water and the amount of water in the reaction system within the range of 0.02 moles or less per mole of the aprotic polar organic solvent, What is obtained by the method of making it react (refer pamphlet of WO2010 / 058713) 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 a fatty acid ester (B) as an essential component. The fatty acid ester (B) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but an esterified product of a long-chain fatty acid having 12 or more carbon atoms and an alcohol is used. In particular, it is more preferable to use an esterified product of a long-chain fatty acid having 20 to 30 carbon atoms and an alcohol. As these fatty acids, saturated fatty acids, unsaturated fatty acids, and derivatives thereof can be used, but it is particularly preferable to use saturated fatty acids. Examples of the fatty acid contained in the fatty acid ester (B) used in the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicin It is preferable to use acid, adipic acid, sebacic acid, and derivatives thereof, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and derivatives thereof are more preferable, behenic acid, montanic acid and These derivatives are particularly preferred.

Examples of the alcohol include monohydric alcohols and polyhydric alcohols, among which polyhydric alcohols are preferred. The monohydric alcohol is preferably an alcohol having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and examples thereof include methanol, ethanol, butanol, 2-ethylhexanol, stearyl alcohol and the like. Examples of the polyhydric alcohol include polyhydric alcohols having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, or polymers thereof such as alkylene glycol (ethylene glycol, diethylene glycol, propylene glycol, etc.). Diols; triols such as glycerin, trimethylolpropane or derivatives thereof; tetraols such as pentaerythritol, sorbitan or derivatives thereof; and these polyhydric alcohols alone or as copolymers (for example, polyethylene glycol, And a polyoxyalkylene glycol such as polypropylene glycol or a copolymer, polyglycerin, etc.). The average degree of polymerization of the polyoxyalkylene glycol is 2 or more (for example, in the range of 2 to 500), preferably in the range of 2 to 400, more preferably the average degree of polymerization of 16 or more, preferably in the range of 20 to 200. . When polyoxyalkylene glycol is used as the polyhydric alcohol, the fatty acid constituting the ester is a fatty acid having a carbon number of 12 or more, for example, saturated or unsaturated having a monovalent carbon number of 12 to 26 It is preferable to use fatty acids, saturated or unsaturated fatty acids having a divalent carbon number of 12 to 20, and the like.

Examples of such fatty acid esters include ethylene glycol distearate, ethylene glycol dimontanate, glycerol monostearate, glycerol tripalmitate, polyglycerol tristearate, trimethylolpropane monopalmitate, Pentaerythritol monoundecylate, sorbitan monostearate, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) monolaurate, monopalmitate, monostearate, dilaurate, dipalmitate, distearate, dibehenate, dimontanate, dioleate, Examples include dilinoleate. Specific examples of such fatty acid ester (B) include montanic acid ester wax (manufactured by Clariant Japan Co., Ltd. “Recolbe WE4” acid value 29 mg KOH / g, dropping point 81 ° C.), montanic acid ester wax (manufactured by Clariant Japan Co., Ltd.). "Ricolbu E" acid value 17 mgKOH / g, drop point 83 ° C), Montanate ester wax ("Clollive WE40" acid value 17 mgKOH / g, drop point 75 ° C by Clariant Japan KK), Montanate ester wax (Clariant Japan shares) Examples include the use of “Recolum WM31” manufactured by the company, acid value 12 mgKOH / g, dropping point 75 ° C.).

酸 The acid value of the fatty acid ester (B) used in the present invention is not particularly limited as long as the effect of the present invention is exhibited. The lower limit of the acid value of the fatty acid ester (B) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and particularly preferably 10 mgKOH / g or more. In addition, the upper limit of the acid value of the fatty acid ester (B) is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g. When the acid value is in the above range, the adhesion between the molded product obtained by molding the polyarylene sulfide resin composition of the present invention and the epoxy resin is particularly improved, which is preferable. The acid value can be measured by a method based on JISＪK 0070. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize the free fatty acid contained in 1 g of wax.

The dropping point of the fatty acid ester (B) used in the present invention is preferably in the range of 50 ° C. or higher, more preferably in the range of 60 ° C. or higher, and most preferably in the range of 70 ° C. or higher. On the other hand, the upper limit of the dropping point is preferably in the range of 100 ° C. or lower, more preferably in the range of 90 ° C. or lower, and most preferably in the range of 85 ° C. or lower. The dropping point can be measured by a method based on ASTM D127. Specifically, using a metal nipple, it is measured as the temperature at which molten wax first drops from the metal nipple. In the following examples, it can be measured by the same method. When the dropping point is within the above range, the fatty acid ester (B) not only improves the mold releasability of the molded product from the mold, but also suitably affects the continuous moldability. Furthermore, when it is within the above range, the fatty acid ester (B) tends to ooze out on the surface of the molded product. Further, when the polyarylene sulfide resin composition is melt-kneaded, the fatty acid ester (B) is sufficiently melted. Thereby, fatty acid ester (B) disperses | distributes substantially uniformly in a molding. Therefore, segregation of the fatty acid ester (B) on the surface of the molded product is suppressed, and the deterioration of the mold stain and the appearance of the molded product can be reduced.

The content of the fatty acid ester (B) in the polyarylene sulfide resin composition is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is preferably in the range of -4.5 parts by mass, more preferably in the range of 0.1-4 parts by mass. When it is within the above range, it is excellent in epoxy resin adhesion while being excellent in mold releasability from the mold. In addition, it is possible to suppress deterioration of the mold and the appearance of the molded product during molding.

The polyarylene sulfide resin composition of the present invention contains one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts as essential components.

The fatty acid metal salt (C) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is preferable to use a salt of a long chain fatty acid having a carbon number of 12 or more. In particular, it is more preferable to use a salt of a long-chain fatty acid having 20 to 30 carbon atoms. As these fatty acids, saturated fatty acids, unsaturated fatty acids, and derivatives thereof can be used, but it is particularly preferable to use saturated fatty acids. Fatty acids contained in the fatty acid metal salt (C) used in the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, Melicic acid, adipic acid, sebacic acid, and derivatives thereof are preferably used, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melissic acid, and derivatives thereof are more preferable, behenic acid, montanic acid And their derivatives are particularly preferred.

The salt contained in the fatty acid metal salt (C) used in the present invention is one or more fatty acid metal salts selected from alkali metal salts and / or fatty acid alkali metal earth salts, and exhibits the effects of the present invention. It is not particularly limited as long as it is one or more selected from the group consisting of alkali metals such as potassium, sodium and lithium, and alkaline earth metals such as calcium, magnesium and barium, and further potassium and sodium Particularly preferred are fatty acid metal salts containing one or more salts selected from calcium, lithium. When these fatty acid metal salts are used, the ring opening of the epoxy group in the curable resin composition containing the epoxy resin is promoted on the surface of the molded article formed by molding the polyarylene sulfide resin composition. preferable.

The content of one or more fatty acid metal salts (C) selected from the group consisting of alkali metal salts and fatty acid alkali metal earth salts in the polyarylene sulfide resin composition is 100 parts by mass of the polyarylene sulfide resin (A). Is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.05 to 4.5 parts by mass, and most preferably in the range of 0.1 to 4 parts by mass. When the blending amount of the fatty acid metal salt (C) is within the above range, the adhesiveness with the epoxy resin can be improved, and the releasability from the mold at the time of molding can be improved.

The polyarylene sulfide resin composition of the present invention can contain a filler as an optional component, if necessary. As these fillers, known and commonly used 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. A filler etc. are mentioned. Specifically, fiber fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, etc., natural fiber, etc. Glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber Non-fibrous fillers such as calcium sulfate can also be used.

In the present invention, the filler is not an essential component, and when added, the content is not particularly limited as long as the effect of the present invention is not impaired. The content of the filler is, for example, preferably in the range of 1 to 600 parts by mass, more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). . In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

The polyarylene sulfide resin composition of the present invention can contain a silane coupling agent as an optional component, if necessary. 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. 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 in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass. 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 of the present invention can contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among 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 in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). Preferably, it is more preferably in the range of 0.1 to 5 parts by mass. 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. As the functional group, a carboxy group, an acid anhydride group represented by the formula — (CO) O (CO) —, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group Etc.

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, in addition to the above components, the polyarylene sulfide resin composition of the present invention may further comprise a polyester resin, a polyamide resin, a polyimide resin, a polyetherimide resin, a polycarbonate resin, a polyphenylene ether resin, a polysulfone, depending on the intended use. Resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin Further, synthetic resins such as urethane resins and liquid crystal polymers can be contained as optional components. Further, the content of these resins varies depending on the purpose and cannot be specified in general, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In order not to impair the effects of the present invention, it may be appropriately adjusted according to the purpose and application.

In addition, the polyarylene sulfide resin composition of the present invention includes other colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant aids, You may contain well-known and usual additives, such as a rust agent and a coupling agent, as an arbitrary component as needed. These additives are not essential components. For example, they are preferably in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A) so that the effects of the present invention are not impaired. It may be adjusted as appropriate according to the conditions.

The method for producing the polyarylene sulfide resin composition of the present invention comprises at least one selected from the group consisting of polyarylene sulfide resin (A), fatty acid ester (B), fatty acid alkali metal salt and fatty acid alkali metal earth salt. The fatty acid metal salt (C) as an essential component is melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A).

The preferable manufacturing method of the polyarylene sulfide resin composition of the present invention is such that each of the essential components of the polyarylene sulfide resin (A), the fatty acid ester (B), and the fatty acid metal salt (C) is used so as to have the above-described content. , If necessary, optional components such as fillers are put in various forms such as powder, pellets, strips, ribbon blender, Henschel mixer, V blender, etc., dry blended, then Banbury mixer, mixing roll, A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range in which the melting point is + 10 ° C. or higher, more preferably Temperature range of melting point + 10 ° C. to melting point + 100 ° C., more preferably temperature of melting point +20 to melting point + 50 ° C. It can be manufactured through a step of melt-kneading in a range. 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 viewpoint of dispersibility and productivity. For example, the resin component discharge rate is in the range of 5 to 500 (kg / hr), and the screw rotational speed is 50 to 500 (rpm). It is preferable to melt-knead while appropriately adjusting the range of the above, and melt-knead under conditions where the ratio (discharge amount / screw rotation number) is in the range of 0.02 to 5 (kg / hr / rpm) Is more preferable. Moreover, when adding a filler and an additive among the said components, it is preferable from a dispersible viewpoint to throw in into this extruder from the side feeder of the said biaxial kneading extruder. The position of the side feeder is preferably 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 twin-screw kneading extruder is in the range of 0.1 to 0.9. In particular, the range of 0.3 to 0.7 is particularly preferable.

Thus, the polyarylene sulfide resin composition of the present invention obtained by melt-kneading comprises the polyarylene sulfide resin (A), the fatty acid ester (B), the fatty acid alkali metal salt and the fatty acid alkali metal earth, which are essential components. It is a molten mixture containing one or more fatty acid metal salts (C) selected from the group consisting of salts, optional components added as necessary, and components derived therefrom, and after the melt-kneading, pellets, chips, After being processed into a form such as a granule or powder, it is preferably subjected to preliminary drying at a temperature of 100 to 150 ° C., if necessary, and used for various moldings.

The polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and the fatty acid ester (B) and the aliphatic metal salt (C) as essential components in the matrix. And a morphology having a structure in which components derived therefrom and optional components added as necessary are dispersed. As a result, not only the epoxy resin adhesion of the molded product and the MD direction but also the mechanical strength in the TD direction, in particular, the bending elongation strength in the TD direction, becomes favorable, which is preferable.

The reason why the polyarylene sulfide resin molded article of the present invention exhibits excellent adhesion to a curable resin composition containing an epoxy resin is not limited to a specific mechanism of action, but the following may be considered. sell. That is, on the surface of the molded article of the present invention, a carboxylate anion (—COO ⁻ ) derived from a functional group present in the fatty acid ester (B) and the aliphatic metal salt (C) serves as a basic catalyst (nucleophile). , By acting on the carbon atom of the epoxy group derived from the epoxy resin in the curable resin composition to promote the ring opening of the epoxy group, the reactivity of the epoxy group is improved, and the aliphatic metal salt (C ) Is an alkali metal atom or an alkali metal earth atom, for example, ionization energy is small even when compared with other metal atoms of the periodic table such as zinc atom (Zn), and tends to dissociate. Therefore, as a result of generating more carboxylate anions and promoting the ring opening of the epoxy group as described above, the reactivity of the epoxy group can be further improved, Epoxy resin adhesive is considered to have improved.

The polyarylene sulfide resin composition of the present invention can be subjected to various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent properties. In the case of molding by injection 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 in the temperature range above the melting point of the polyarylene sulfide resin, preferably in the temperature range above the melting point + 10 ° C., more preferably in the temperature range from the melting point + 10 ° C. to the melting point + 100 ° C., more preferably the melting point. After passing through the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to melting point + 50 ° C., the resin discharge port may be injected into the mold and molded. At this time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.

The molded product formed by molding the polyarylene sulfide resin composition of the present invention not only has excellent adhesion to an epoxy resin, but also improves the bending elongation of the resin, particularly in the TD direction, and moldability during injection molding. Can do.

The composition of the present invention is excellent in 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 and novolac-type epoxy resins. Among these, bisphenol-type resins are excellent in adhesion. An epoxy resin is mentioned as a preferable thing.

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 are preferably used after being cured with a curing agent.

In the present invention, the curing agent for curing the epoxy resin is not particularly limited as long as it is generally used as a curing agent for the epoxy resin. For example, an amine type curing agent, a phenol resin type curing agent, An acid anhydride type hardening | curing agent, a latent hardening agent, etc. are mentioned.

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 can be obtained, 0.7 to 1.5 equivalents of active groups in the curing agent with respect to a total of 1 equivalent of epoxy groups in the epoxy resin component The amount to be is preferred.

Since the molded product formed by molding the polyarylene sulfide resin composition of the present invention is excellent in adhesiveness to the epoxy resin, the polyarylene sulfide resin and the cured product of the curable resin composition containing the epoxy resin are bonded. It can be suitably used as a composite molded article.
The production method may be a known method as long as the effects of the present invention are not impaired, but a molded product formed by molding a polyarylene sulfide resin composition and a curable resin composition containing an epoxy resin are brought into contact with each other. And a method of curing the curable resin composition.

Examples of the main applications of the composite molded body include housings for electronic devices such as various home appliances, mobile phones, and PCs (Personal Computers), protective / support members for box-shaped electrical / electronic component integrated modules, a plurality of Individual semiconductor or module, 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 , Microphones, 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, iron, hair dryer Ears, rice cooker parts, microwave oven parts, acoustic 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, Or home appliances such as water heaters, bath water, temperature sensors, and other water appliance parts; office computer parts; office computer parts; telephone parts; facsimile parts; copier parts; Machine-related parts represented by tools, motor parts, writers, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, brush holders, slip rings, IC regulator for light diamond Various valves such as tensiometer 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, coolant 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, radiator motor Brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch Ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter relay, transmission wiring harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, horn terminal, electrical component insulation plate It can also be applied to automobile / vehicle-related parts such as step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, and other various applications.

<Examples 1 to 9 and Comparative Examples 1 to 6>
Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all in mass units) described in Tables 1 to 3. Thereafter, the compounded 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 250 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) was melt kneaded at a set resin temperature of 330 ° C. to obtain resin composition pellets. The following various evaluation tests were performed using this pellet. The results of the test and evaluation are shown in Tables 1 to 3.

[Adhesive strength of PAS resin composition to epoxy resin]
The obtained pellets were supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO · MIII) set at a cylinder temperature of 320 ° C., and an ASTM No. 1 dumbbell mold was used to control the mold temperature to 130 ° C. Injection molding was performed to obtain ASTM No. 1 dumbbell pieces. The obtained ASTM No. 1 dumbbell piece was divided into two equal parts from the center, and a spacer (thickness: 1.8 to 2.2 mm, thickness) prepared so that the contact area with the curable resin composition containing an epoxy resin was 50 mm ² . Clamped between two ASTM No. 1 dumbbell pieces divided into two equal parts (opening: 5 mm × 10 mm), fixed using clips, and then curable resin composition containing epoxy resin in the opening (two liquids manufactured by Nagase ChemteX Corporation) Type epoxy resin, main agent: XNR5002, curing agent: XNH5002, blending ratio was main agent: curing agent = 100: 90), and heated and cured and 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 using the obtained test piece, the strain rate was 1 mm / min, the distance between fulcrums was 80 mm, and the tensile strength at break was measured at 23 ° C. using a Shimadzu tensile tester. The value divided by the adhesion area was defined as the epoxy adhesion strength.

[TD direction bending elongation]
The obtained pellets were supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO · MIII) set at a cylinder temperature of 320 ° C., using an ISO D2 plate molding die adjusted to a mold temperature of 130 ° C. Injection molding was performed and the specimen was cut into an ISO D2 plate. The obtained test piece was measured for TD bending strength and TD bending elongation by a measuring method based on ISO178.

In Tables 1 to 3, the blending ratio of the blended resins and materials represents parts by mass, and the followings were used.
A1: Polyphenylene sulfide (“LR-2G” manufactured by DIC Corporation, melt viscosity (V6) 80 [Pa · s])
A2: Polyphenylene sulfide (“T-2G” manufactured by DIC Corporation, melt viscosity (V6) 55 [Pa · s])
B1: Montanic acid ester wax (Clariant Japan Co., Ltd. “Ricolb WE4” acid value 29 mg KOH / g, dropping point 81 ° C.)
B2: Montanic acid ester wax (Clariant Japan Co., Ltd. “Recolbe WM31” acid value 12 mg KOH / g, dropping point 75 ° C.)
b3: Linear polyethylene wax (“Licowax PE 130” manufactured by Clariant Japan KK, acid value 0 mgKOH / g)
C1: Calcium montanate (“CaV-102” manufactured by Clariant Japan Co., Ltd.)
C2: sodium montanate (“NaV-101” manufactured by Clariant Japan Co., Ltd.)
C3: Calcium behenate (“CS-7” manufactured by Nitto Kasei Kogyo Co., Ltd.)
C4: Lithium 12-hydroxystearate (“LS-6” manufactured by Nitto Kasei Kogyo Co., Ltd.)
D1: Glass fiber (glass fiber chopped strand having a fiber diameter of 10 μm and a length of 3 mm)
D2: Calcium carbonate (average particle size 5 [μm])

Claims

The polyarylene sulfide resin (A), the fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts are contained as essential components. ,
The fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). A polyarylene sulfide resin composition characterized by being in a range.
The polyarylene sulfide resin composition according to claim 1, wherein the fatty acid metal salt (C) is a long chain fatty acid salt having 20 or more carbon atoms.
The polyarylene sulfide resin composition according to claim 1, which is a melt-kneaded product.
A molded product formed by molding the polyarylene sulfide resin composition according to any one of claims 1 to 3.
A composite molded product obtained by bonding the molded product according to claim 4 and a cured product of a curable resin composition containing an epoxy resin.
A polyarylene sulfide resin (A), a fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts as essential components A method for producing a polyarylene sulfide resin composition, characterized by melting and kneading at a melting point or higher of the sulfide resin (A).
The fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). The manufacturing method of the polyarylene sulfide resin composition of Claim 6 which is a range.
A method for producing a composite molded product, comprising: contacting the molded product according to claim 4 with a curable resin composition containing an epoxy resin, and then curing the curable resin composition.