TW201510088A - Polyarylene sulfide resin composition and molded article thereof - Google Patents

Abstract

The invention discloses a polyarylene sulfide resin composition, which includes the polyarylene sulfide resin, and at least one other component selected from a group consisted of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinking resin having two or more crosslinking functional groups. The polyarylene sulfide resin may be obtained by a method including a step of reacting a diiodoaromatic compound, the elemental sulfur with a polymerization inhibitor having a group represented by the following formula (1) in a melting mixture including the diiodoaromatic compound, the elemental sulfur and the polymerization inhibitor. (In the formula, X represents a hydrogen atom or an alkali metal atom.).

Description

Polyarylene sulfide resin composition and molded article thereof

The present invention relates to a polyarylene sulfide resin composition and a molded article thereof.

In recent years, in various fields represented by the field of electrical and electronic components, the development of low-halogenation has become more active as a countermeasure against the environment.

A polyarylene sulfide resin (hereinafter sometimes abbreviated as "PAS resin") typified by a polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS resin") may be used without using a halogen. The flame retardant is also highly flame-retardant, and is therefore attracting attention as a halogen free material.

The polyphenylene sulfide resin can be produced, for example, by solution polymerization in which p-dichlorobenzene and sodium sulfide, or sodium hydrosulfide and sodium hydroxide are used as a raw material to carry out polymerization in an organic polar solvent (for example, Refer to Patent Document 1 and Patent Document 2). Commercially available polyphenylene sulfide resins are usually produced by this method.

However, since the polymerization product obtained by this method usually contains by-products such as sodium chloride and an organic polar solvent, a purification treatment for removing these is required. In addition, even if the refining treatment is performed, it is difficult to sufficiently remove the chlorine atoms in the resin. It is not uncommon.

In another method for producing a polyarylene sulfide resin, there is known a method in which a diiodo aromatic compound and elemental sulfur are melt-polymerized without using a raw material containing a chlorine atom and a polar solvent (see Patent Document 3, Patent Document 4, and Patent). Document 5). Although the polyarylene sulfide resin obtained by this method contains an iodine atom, for example, the iodine atom can be sufficiently easily removed by heating the polymerization reaction product or the crude product after the polymerization reaction under reduced pressure to sublimate iodine. Low concentration. That is, according to the method using melt polymerization, it is expected that a polyarylene sulfide resin which does not substantially contain chlorine atoms and sufficiently reduces the concentration of halogen atoms can be easily produced.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] US Patent No. 2,513,188

[Patent Document 2] US Patent No. 2,583,941

[Patent Document 3] US Patent No. 4,746,758

[Patent Document 4] US Patent No. 4,786,713

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2010-501661

However, in the polyarylene sulfide resin obtained by the method of melt polymerization, the amount of gas generated by heating during molding processing is relatively large, and further improvement is required in this respect. In particular, the polyarylene sulfide resin is mixed with other materials such as an inorganic filler, various thermoplastic resins, and elastomers. In the prepared resin composition, there is a tendency that the problem of gas generation becomes remarkable. When the amount of gas generated is large, there is a possibility that the quality of the molded article is lowered. Therefore, suppression of gas generation is very important for the molding material.

Therefore, the main object of the present invention is to suppress the generation of gas by heating by using a resin composition of a polyarylene sulfide resin obtained by a method of melt-polymerizing a diiodo aromatic compound and elemental sulfur. the amount.

The inventors of the present invention conducted various studies and found that it can be solved by using a polymerization inhibitor having a specific functional group in a method for producing a polyarylene sulfide resin in which a diiodo aromatic compound and elemental sulfur are melt-polymerized. The subject matter described above has thus completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin composition comprising a polyarylene sulfide resin, and a thermoplastic resin selected from the group consisting of an inorganic filler, the polyarylene sulfide resin, an elastomer, and two At least one other component (hereinafter, simply referred to as "the other component") of the group consisting of the crosslinkable resin of the above crosslinkable functional group. The polyarylene sulfide resin can include the diiodo aromatic compound, a polymerization inhibitor including a diiodo aromatic compound, elemental sulfur, and a group represented by the following formula (1). It is obtained by the method of the step of reacting the elemental sulfur and the molten mixture of the polymerization inhibitor.

(wherein X represents a hydrogen atom or an alkali metal atom)

According to the present invention, the resin composition of the polyarylene sulfide resin obtained by the method of melt-polymerizing a diiodo aromatic compound and elemental sulfur can suppress the amount of gas generated by heating for forming or the like. .

The polyarylene sulfide resin composition of the present invention can be a substance which substantially does not contain a chlorine atom and sufficiently reduces the concentration of a halogen atom. Further, the polyarylene sulfide resin composition of the present invention is based on a polyarylene sulfide resin and other components selected from the group consisting of inorganic fillers, thermoplastic resins, elastomers, and crosslinkable resins having two or more crosslinkable functional groups. The combination can exhibit excellent characteristics in terms of mechanical properties, acid resistance, alkali resistance, hot water resistance, and cavity balance. The cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded articles are simultaneously formed by injection molding using a mold having a plurality of cavities. When the cavity balance of the molding material is insufficient, there is a tendency that a molding failure in which a part of the cavity is not sufficiently filled is likely to occur.

Hereinafter, preferred embodiments of the present invention will be described in detail. but However, the present invention is not limited to the following embodiments.

The polyarylene sulfide resin composition of the present embodiment contains a polyarylene sulfide resin such as a polyphenylene sulfide resin. The polyarylene sulfide resin can be made into a diiodo aromatic compound by being contained in a molten mixture containing a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor having a group represented by the following formula (1). Obtained by a method of the step of reacting elemental sulfur and a polymerization inhibitor.

(wherein X represents a hydrogen atom or an alkali metal atom)

The diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to the aromatic ring. Examples of the diiodo aromatic compound include diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether, and diiododiphenylphosphonium. , but not limited to these. The substitution position of the two iodine atoms is not particularly limited, and it is preferred that the two substitution positions are located as far as possible within the molecule. Preferred substitution positions are the para position and the 4,4'-position.

The aromatic ring of the diiodo aromatic compound may also be a halogen atom selected from a phenyl group or an iodine atom, a hydroxyl group, a nitro group, an amine group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carboxylate group, and an aromatic group. Substituting at least one substituent in the quinone and aryl ketone. Among them, the substituted diiodide is used in terms of crystallinity and heat resistance of the polyarylene sulfide resin. The ratio of the aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001% by mass to 5% by mass, and more preferably in the range of 0.001% by mass to 1% by mass.

Elemental sulfur means a substance composed only of sulfur atoms (S ₈ , S ₆ , S ₄ , S _{2 ,} etc.), and its form is not limited. Specifically, elemental sulfur which is commercially available as a pharmaceutical product prescribed by the Japanese Pharmacopoeia Law can be used, and a mixture containing S ₈ and S ₆ which can be obtained in a general manner can also be used. The purity of elemental sulfur is also not particularly limited. If the elemental sulfur is a solid at room temperature (23 ° C), it may be in the form of a pellet or a powder. The particle size of the elemental sulfur is not particularly limited, but is preferably in the range of 0.001 mm to 10 mm, more preferably in the range of 0.01 mm to 5 mm, and still more preferably in the range of 0.01 mm to 3 mm.

The polymerization inhibitor having a group represented by the formula (1) (hereinafter, simply referred to as "polymerization inhibitor") may have one or two or more groups represented by the formula (1), and The compound which inhibits or terminates the polymerization reaction in the polymerization reaction of the thioether resin can be used without particular limitation. The polymerization inhibitor may be, for example, selected from the group consisting of diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl Of 2-benzothiazolylsulfinamide, 2-(morpholinylthio)benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazol-2-sulfinamide At least one compound and having the group represented by the above formula (1) bonded directly or via another partial structure to its conjugated aromatic ring. If necessary, the polymerization inhibitor may be used in combination with a compound having no group represented by the formula (1).

X in the formula (1) is a hydrogen atom or an alkali metal atom, and is preferably a hydrogen atom from the viewpoint that the reactivity is good. Examples of the alkali metal atom include sodium and lithium. Potassium, strontium, barium, etc., but preferably sodium.

The polymerization inhibitor is preferably one or more compounds selected from the group consisting of compounds represented by the following formula (2), formula (3) or formula (4).

In the formula (2), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following formula (a), formula (b) or formula (c), R ¹ or R At least one of ² is a monovalent group represented by the formula (a), the formula (b) or the formula (c). In the formula (3), Z represents an iodine atom or a fluorenyl group, and R ³ represents a monovalent value represented by the following formula (a), formula (b) or formula (c). In the formula (4), R ⁴ represents a monovalent group represented by the formula (a), the formula (b) or the formula (c).

X in the formulae (a) to (c) also includes the preferred forms thereof and has the same meaning as X in the formula (1). In the formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In the formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms.

The polyarylene sulfide resin of the present embodiment is to contain a diiodide aromatic A molten mixture obtained by heating a mixture of a compound, elemental sulfur, a polymerization inhibitor, and an optional catalyst is produced by melt polymerization. The proportion of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 mol to 2 mol, more preferably in the range of 0.8 mol to 1.2 mol, based on the elemental sulfur 1 mol. Further, the ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 mol to 0.1 mol, more preferably in the range of 0.0005 to 0.05, relative to the solid sulfur 1 mol.

The period in which the polymerization inhibitor is added is not particularly limited, and a mixture containing a diiodide aromatic compound, elemental sulfur, and optionally a catalyst may be heated, and the temperature of the mixture is preferably in the range of 200 ° C to 320 ° C. More preferably, a polymerization inhibitor is added at a time point in the range of 250 ° C to 320 ° C.

A nitro compound can be added to the molten mixture as a catalyst to adjust the polymerization rate. As the nitro compound, various nitrobenzene derivatives can be usually used. Examples of the nitrobenzene derivative include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, and 2,6-di Iodine-4-nitroamine. The amount of the catalyst is usually an amount to be added as a catalyst. For example, it is preferably in the range of 0.01 part by mass to 20 parts by mass based on 100 parts by mass of the elemental sulfur.

The conditions of the melt polymerization can be suitably adjusted in such a manner that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably 175 ° C or higher and the melting point of the produced polyarylene sulfide resin is +100 ° C or lower, more preferably 180 ° C to 350 ° C. The melt polymerization is carried out in a range where the absolute pressure is preferably from 1 [cPa] to 100 [kPa], more preferably from 13 [cPa] to 60 [kPa]. The conditions of the melt polymerization need not be fixed. For example, the temperature may be preferably in the range of preferably 175 ° C to 270 ° C, more preferably 180 ° C in the initial stage of polymerization. In the range of ～250°C, the absolute pressure is set to be in the range of 6.7 [kPa] to 100 [kPa], and then the polymerization is carried out while continuously or in a stepwise manner, and the temperature is set to be post-polymerization. It is preferably 270 ° C or higher and the melting point of the produced polyarylene sulfide resin is in the range of +100 ° C or lower, more preferably in the range of 300 ° C to 350 ° C, and the absolute pressure is set to 1 [cPa] to 6 [kPa]. Aggregate the scope. In the present specification, the melting point of the resin means a DSC (differential scanning calorimeter) device manufactured by PerkinElmer (Pyris Diamond) according to the Japanese Industrial Standard (Japanese). Industrial Standards, JIS) K 7121 and measured values.

From the viewpoint of preventing the oxidative crosslinking reaction and obtaining a high degree of polymerization, the melt polymerization is preferably carried out in a non-oxidizing atmosphere. In a non-oxidizing environment, the oxygen concentration in the gas phase is preferably less than 5% by volume, more preferably less than 2% by volume, and further preferably the gas phase is substantially free of oxygen. The non-oxidizing environment is preferably an inert gas atmosphere such as nitrogen, helium or argon.

The melt polymerization can be carried out, for example, using a melt kneader equipped with a heating device, a pressure reducing device, and a stirring device. Examples of the melt kneading machine include a Banbury mixer, a kneader, a continuous kneader, a single-screw extruder, and a twin-screw extruder.

The molten mixture for melt polymerization is preferably substantially free of solvent. More specifically, the amount of the solvent contained in the molten mixture is preferably 10 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the diiodide aromatic compound, the elemental sulfur, the polymerization inhibitor, and the optional catalyst. Preferably 5 parts by mass or less, and further preferably 1 mass The following. The amount of the solvent may be 0 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more.

After the molten mixture (reaction product) after melt polymerization is cooled to obtain a mixture in a solid state, the mixture is heated under reduced pressure or atmospheric pressure in a non-oxidizing atmosphere to further carry out the polymerization reaction. Thereby, not only the molecular weight can be further increased, but also the generated iodine molecules can be sublimated and removed, so that the concentration of iodine atoms in the polyarylene sulfide resin can be suppressed to be low. The mixture in a solid state can be obtained by cooling to a temperature of preferably from 100 ° C to 260 ° C, more preferably from 130 ° C to 250 ° C, and still more preferably from 150 ° C to 230 ° C. The heating after cooling to a solid state can be carried out under the same temperature and pressure conditions as the melt polymerization.

The reaction product containing the polyarylene sulfide resin obtained by the melt polymerization step can also be used to produce a resin composition by directly feeding it into a melt kneader in this state, but it is preferred to add and dissolve the reaction product. The solvent of the reaction product is used to prepare a lysate, and the reaction product is extracted from the reaction apparatus in the state of the lysate, because the productivity is excellent and the reactivity is also good. The addition of the solvent for dissolving the reaction product is preferably carried out after the melt polymerization, but may be carried out later in the reaction of the melt polymerization, or may be obtained by cooling the molten mixture (reaction product) as described above to obtain a solid state. After the mixture is heated under pressure, under reduced pressure, or under a non-oxidizing atmosphere, the polymerization reaction is further carried out. The step of preparing the solute can also be carried out in a non-oxidizing environment. In addition, the temperature at which the heat is dissolved is only a solvent which dissolves the reaction product. The range of the melting point or more may be, preferably in the range of 200 ° C to 350 ° C, more preferably in the range of 210 ° C to 250 ° C, and it is preferably carried out under pressure.

The blending ratio of the solvent for preparing the solute and dissolving the reaction product is preferably from 90 parts by mass to 1000 parts by mass, more preferably from 90 parts by mass to 1000 parts by mass, based on 100 parts by mass of the reaction product containing the polyarylene sulfide resin. A range of 200 parts by mass to 400 parts by mass.

The solvent which dissolves the reaction product can be, for example, a solvent used as a polymerization solvent in solution polymerization such as the Phillips method. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethylene. Aliphatic cyclic guanamine compounds such as keto-2-imidazolidinone, ε-caprolactam, N-methyl-ε-caprolactam, trimethylamine hexamethylphosphate (HMPA), tetramethyl A guanamine compound such as urea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA), polyethylene glycol dialkyl ether (degree of polymerization of 2000 or less, and carbon number 1) An etherified polyethylene glycol compound such as an alkyl group of ~20), and an anthracene compound such as tetramethylenefluorene or dimethylarylene (DMSO). Examples of other solvent which can be used include one or more solvents selected from the group consisting of benzophenone, diphenyl ether, diphenyl sulfide, 4,4'-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-diphenyloxazole, triphenylmethanol, N,N-diphenylformamide, Benzophenone, anthracene, 4-benzylidenebiphenyl, benzhydrylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, 1-benzyl-2-pyrroledione, 9 -fluorenone, 2-benzylidene naphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, anthracene, 1-phenyl-2-pyrrolidone, 1-methoxynaphthalene, 1-B Oxynaphthalene, 1,3-diphenylacetone, 1,4-Diphenylmercaptobutane, phenanthrene, 4-benzylidenebiphenyl, 1,1-diphenylacetone, o-, o-'-biphenol, 2,6-diphenylphenol, Triphenylene, 2-phenylphenol, thiophene, 3-phenoxybenzyl alcohol, 4-phenylphenol, 9,10-dichloropurine, triphenylmethane, 4,4'-dimethoxy Benzophenone, 9,10-diphenylfluorene, fluoranthene, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxy Naphthalene, 4-bromodiphenyl ether, hydrazine, 9,9'-bi-indole, 4,4'-isopropylidene-diphenol, epsilon-caprolactam, N-cyclohexyl- 2-pyrrolidone, diphenyl isophthalate and diphenyl terephthalate and 1-chloronaphthalene.

The dissolved material extracted from the reaction apparatus is preferably subjected to post-treatment, and is melt-kneaded with the other components to prepare a resin composition because the reactivity is further improved. The method of post-treatment of the dissolved matter is not particularly limited, and examples thereof include the following methods.

(1) The solute is directly or after adding an acid or a base, the solvent is distilled off under reduced pressure or under normal pressure, and then the solid matter obtained by distilling off the solvent is selected from water selected from the lysate. The solvent (or an organic solvent having the same solubility for a low molecular weight polymer), the solvent in acetone, methyl ethyl ketone, and an alcohol or the like is washed once or twice, and further neutralized and washed. , filtration and drying methods.

(2) adding a solvent such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon, or aliphatic hydrocarbon to the solute (a solvent soluble in the solute, and at least for the poly The aryl sulfide resin is a solvent of a poor solvent. As a precipitant, a solid product containing a polyarylene sulfide resin, an inorganic salt or the like is precipitated, and a solid product is obtained. A method of separating, washing, and drying by filtration.

(3) adding a solvent (or an organic solvent having an equivalent solubility to a low molecular weight polymer) to the solute, stirring the mixture, and filtering the low molecular weight polymer to remove the The solvent in acetone, methyl ethyl ketone, and alcohol is washed once or twice, and then neutralized, washed with water, filtered, and dried.

Further, in the post-treatment method as exemplified in the above (1) to (3), the drying of the polyarylene sulfide resin may be carried out in a vacuum, or may be carried out in the air or in an inert gas atmosphere such as nitrogen. The polyarylene sulfide resin may be subjected to oxidative crosslinking by performing heat treatment in an oxidizing atmosphere or a reduced pressure condition in an oxygen concentration of from 5% by volume to 30% by volume.

The reaction of producing a polyarylene sulfide resin having a group represented by the formula (1) at the end by melt polymerization is exemplified below.

The reaction formula (1) to the reaction formula (5) are examples of a reaction for producing polyphenylene sulfide using a diphenyl disulfide having a substituent R containing a group represented by the formula (1) as a polymerization inhibitor. . The reaction formula (1) is a reaction in which a -S-S- bond in a polymerization inhibitor undergoes radical cracking at a melting temperature. The reaction formula (2) is that the sulfur radical generated in the reaction formula (1) attacks the adjacent carbon atom of the terminal iodine atom of the growing main chain to liberate the iodine atom, thereby terminating the polymerization, and 1) A reaction in which the indicated group is introduced to the end of the main chain. The reaction formula (3) is a reaction in which a disulfide bond which is derived from a raw material (elemental sulfur) in the main chain of the polyarylene sulfide resin undergoes radical cracking at a melting temperature. The reaction formula (4) terminates the polymerization by re-bonding the sulfur radical generated in the reaction formula (3) with the sulfur radical generated in the reaction formula (1), and is represented by the formula (1). The reaction of the group introduced into the end of the main chain. Take off The separated iodine atoms are in a free state (iodine radical) or are re-bonded to each other by an iodine radical as in the reaction formula (5) to form an iodine molecule.

The reaction product containing a polyarylene sulfide resin obtained by melt polymerization contains an iodine atom derived from a raw material. Therefore, the polyarylene sulfide resin is usually used in the preparation of a resin composition or the like in a state of a mixture containing an iodine atom. The concentration of the iodine atom in the mixture is, for example, in the range of 0.01 ppm to 10,000 ppm with respect to the polyarylene sulfide resin, and preferably in the range of 10 ppm to 5000 ppm. The iodine atom concentration can be suppressed to be low by the sublimation property of the iodine molecule. In this case, the range may be 900 ppm or less, preferably 100 ppm or less, and further 10 ppm or less. Further, although the iodine atom can be removed to the detection limit or less, it is not practical if productivity is considered. The detection limit is, for example, about 0.01 ppm. The polyarylene sulfide resin of the present embodiment obtained by melt polymerization or a reaction product containing the same may be, for example, a solution polymerization of a dichloroaromatic compound such as a Phillips method in an organic polar solvent, in terms of containing an iodine atom. The polyarylene sulfide obtained by the method is clearly distinguished.

As can be understood from the reaction formula, the polyarylene sulfide resin obtained by melt polymerization contains an aromatic ring mainly composed of a diiodo aromatic compound and a sulfur atom directly bonded to the aromatic ring. a main chain composed of an aryl sulfide unit and a group of the formula (1) bonded to the terminal of the main chain. The group of the formula (1) is an aromatic ring bonded to the terminal of the main chain directly or via a partial structure derived from a polymerization inhibitor.

The polyphenylene sulfide resin as the polyarylene sulfide resin of the embodiment has, for example, a main group including a repeating unit (arylene sulfide unit) represented by the following formula (10) chain.

The repeating unit represented by the formula (10) is more preferably a repeating unit represented by the following formula (10a) which is bonded by a para position, and a repeating unit represented by the following formula (10b) which is a meta-bond.

Among these, the repeating unit bonded by the formula represented by the formula (10a) is preferable in terms of heat resistance and crystallinity of the resin.

The polyphenylene sulfide resin of one embodiment may contain a repeating unit having a substituent which is a side chain bonded to an aromatic ring represented by the following formula (11).

(wherein R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amine group, a phenyl group, a methoxy group, or an ethoxy group)

Among them, the polyphenylene sulfide resin preferably contains substantially no repeating unit of the formula (11) from the viewpoint of a decrease in crystallinity and heat resistance. More specifically, the ratio of the repeating unit represented by the formula (11) is preferably 2% by mass or less based on the total of the repeating unit represented by the formula (10) and the repeating unit represented by the formula (11). More preferably, it is 0.2 mass% or less.

The polyarylene sulfide resin of the present embodiment has, for example, a monovalent group represented by the following formula (6) or (7) as a constituent unit of the terminal of the main chain. The presence of the constituent units at the ends of the specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization of the present embodiment.

(wherein R ⁵ represents a monovalent group represented by the formula (a), the formula (b) or the formula (c))

(wherein R ⁶ represents a monovalent group represented by the formula (a), the formula (b) or the formula (c))

The polyarylene sulfide resin of the present embodiment is mainly composed of the arylene sulfide unit, but usually contains a disulfide bond-based constituent unit represented by the following formula (20) which is derived from the elemental sulfur of the raw material in the main chain. .

In terms of heat resistance and mechanical strength, the ratio of the constituent unit represented by the formula (20) is preferably 2.9 mass% or less based on the total of the constituent portions represented by the aryl sulfide unit and the formula (20). The range is preferably 1.2% by mass or less.

The melting point of the polyarylene sulfide resin of the present embodiment is preferably in the range of 250 ° C to 300 ° C, more preferably in the range of 265 ° C to 300 ° C. The melt viscosity (V6) of the polyarylene sulfide resin at 300 ° C is preferably 1 [Pa. s]~2000[Pa. The range of s] is more preferably 5 [Pa. s]~1700[Pa. The scope of s]. Here, the melt viscosity (V6) means using a flow tester at a temperature of 300 ° C and a load of 1.96 MPa. The melt viscosity of the orifice having a ratio of the length of the orifice to the diameter of the orifice (the length of the orifice / the diameter of the orifice) of 10/1 was maintained for 6 minutes.

The polyarylene sulfide resin composition of the present embodiment may contain one or two or more inorganic fillers. By blending an inorganic filler, a composition having high rigidity and high heat resistance stability can be obtained. Examples of the inorganic filler include powdery fillers such as carbon black, calcium carbonate, cerium oxide, and titanium oxide; plate-shaped fillers such as talc and mica; glass beads and cerium oxide. Granular fillers such as beads and glass balloons, fibrous fillers such as glass fibers, carbon fibers and wollastonite fibers, and glass flakes. The polyarylene sulfide resin composition is particularly preferably at least one inorganic filler selected from the group consisting of glass fibers, carbon fibers, carbon black, and calcium carbonate.

The content of the inorganic filler is preferably from 1 part by mass to 300 parts by mass, more preferably from 5 parts by mass to 200 parts by mass, even more preferably from 15 parts by mass to 100 parts by mass per 100 parts by mass of the polyarylene sulfide resin. A range of 150 parts by mass. When the content of the inorganic filler is within these ranges, it is possible to obtain an effect that is more excellent in maintaining the mechanical strength of the molded article.

The polyarylene sulfide resin composition of the present embodiment may contain a resin other than the polyarylene sulfide resin selected from the group consisting of a thermoplastic resin, an elastomer, and a crosslinkable resin. These resins may be blended with the inorganic filler in the resin composition.

The thermoplastic resin to be blended in the composition of the polyarylene sulfide resin may, for example, be a polyester, a polyamide, a polyimine, a polyether quinone, a polycarbonate, a polyphenylene ether, a polyfluorene or a polyether oxime. Polyetheretherketone, polyetherketone, polyethylene, polypropylene, polytetrafluoroethylene Alkene, polyvinylidene fluoride, polystyrene, acrylonitrile butadiene styrene (ABS) resin, anthrone resin, and liquid crystal polymer (liquid crystal polyester, etc.).

Polyamine is a polymer having a guanamine bond (-NHCO-). The polyamine resin may, for example, be (i) a polymer obtained by polycondensation of a diamine and a dicarboxylic acid, (ii) a polymer obtained by polycondensation of an aminocarboxylic acid, and (iii) open from an indoleamine. A polymer obtained by ring polymerization or the like. Polyamine can be used singly or in combination of two or more.

Examples of the diamine for obtaining polyamine may be an aliphatic diamine, an aromatic diamine, and an alicyclic diamine. The aliphatic diamine is preferably a linear or branched diamine having 3 to 18 carbon atoms. Examples of preferred aliphatic diamines include 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-six. Methylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediene Amine, 1,10-decamethylenediamine, 1,11-undecethylenediamine, 1,12-dodeethylenediamine, 1,13-trimethylenediamine, 1, 14-tetramethylmethylenediamine, 1,15-pentadecyldiamine, 1,16-hexamethylenediamine, 1,17-heptadedomethylenediamine, 1,18- Octadecyldiamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. These may be used alone or in combination of two or more.

The aromatic diamine is preferably a diamine having 6 to 27 carbon atoms which has a phenyl group. Examples of preferred aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and 3,4-diamine. Diphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylanthracene, 4,4'- Diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, 4,4'-bis(m-aminophenoxy)diphenylphosphonium, 4,4'-di(p-amine Phenyloxy)diphenylphosphonium, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(4-aminobenzene) Propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4 -aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3- Bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diamino-3,3'-diethyl-5,5' - dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2' - Dimethylbenzidine.

These may be used alone or in combination of two or more.

The alicyclic diamine is preferably a diamine having a carbon number of 4 to 15 having a cyclohexylene group. Examples of preferred alicyclic diamines include: 4,4'-diamino-dicyclohexylmethane, 4,4'-diamino-dicyclohexylpropane, 4,4'-di Amino-3,3'-dimethyl-dicyclohexylmethane, 1,4-diaminocyclohexane, and piperazine. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid used to obtain the polyamine are an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an alicyclic dicarboxylic acid.

The aliphatic dicarboxylic acid is preferably a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms. Examples of preferred aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can be used separately Or use in combination of two or more.

The aromatic dicarboxylic acid is preferably a dicarboxylic acid having a phenyl group and having a carbon number of 8 to 15. Examples of preferred aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, and biphenyl-4,4'. -dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylphosphonium-4,4'-dicarboxylic acid, 2,6- Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, and 1,4-naphthalene dicarboxylic acid. These may be used alone or in combination of two or more. Further, a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, or pyromellitic acid may be used in the range in which melt molding is possible.

The aminocarboxylic acid is preferably an aminocarboxylic acid having 4 to 18 carbon atoms. Examples of preferred aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, and 10-amino group. Capric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These may be used alone or in combination of two or more.

Examples of the indoleamine which is used to obtain polyamine are ε-caprolactam, ω-dodecanamide, hydrazine-heptaneamine, and η-octeneamine. These may be used alone or in combination of two or more.

Preferred combinations of the raw materials of the polyamidamine include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine/adipic acid (nylon 6,6), and 1,4-four. Methylenediamine/adipate (nylon 4,6), 1,6-hexamethylenediamine/terephthalic acid, 1,6-hexamethylenediamine/terephthalic acid/ε- Caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, 1,9-nonamethylenediamine/terephthalic acid, 1,9-nonamethylene Amine/terephthalic acid/ε-caprolactam, 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/ Adipic acid, and m-xylylenediamine/adipic acid. Among these, a polyamide resin obtained by a combination of 1,4-tetramethylenediamine/adipic acid (nylon 4,6) and 1,6-hexamethylenediamine is further preferred. /terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, 1,9-nonamethylenediamine/terephthalic acid, 1 , 9-nonamethylenediamine/terephthalic acid/ε-caprolactam, or 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/ Adipic acid.

The content of the thermoplastic resin is preferably from 1 part by mass to 300 parts by mass, more preferably from 3 parts by mass to 100 parts by mass, even more preferably from 5 parts by mass to 45 parts by mass per 100 parts by mass of the polyarylene sulfide resin. The range of parts by mass. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within these ranges, an effect of further improving heat resistance, chemical resistance, and mechanical properties can be obtained.

The elastomer blended in the polyarylene sulfide resin composition is often a thermoplastic elastomer. Examples of the thermoplastic elastomer include a polyolefin-based elastomer, a fluorine-based elastomer, and an anthrone-based elastomer. Further, in the present specification, the thermoplastic elastomer is classified into an elastomer, not the thermoplastic resin.

The elastomer (particularly a thermoplastic elastomer) preferably has a functional group reactive with a hydroxyl group or an amine group. Thereby, a resin composition which is particularly excellent in adhesion and impact resistance can be obtained. The functional group may, for example, be an epoxy group, a carboxyl group, an isocyanate group, an oxazolinyl group, and a formula: R(CO)O(CO)- or R(CO)O- (wherein R represents a carbon number of 1 a group represented by an alkyl group of ~8). The thermoplastic elastomer having the functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the functional group. Examples of the α-olefin include ethylene, propylene, and butene-1. An α-olefin having 2 to 8 carbon atoms. Examples of the vinyl polymerizable compound having the functional group include α,β-unsaturated carboxylic acids such as (meth)acrylic acid and (meth)acrylate, and alkyl esters thereof, maleic acid, and counter-butylene. Arogate, itaconic acid and other α,β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (monoesters or diesters, their anhydrides, etc.), and glycidol (meth)acrylate Ester and the like. Among these, in terms of improving toughness and impact resistance, it is preferred to have an epoxy group, a carboxyl group, and a formula: R(CO)O(CO)- or R(CO)O-(form). In the above, R represents an ethylene-propylene copolymer and an ethylene-butene copolymer of at least one functional group in the group consisting of groups represented by an alkyl group having 1 to 8 carbon atoms.

The content of the elastomer varies depending on the type and use thereof, and therefore cannot be specified. For example, it is preferably in the range of 1 part by mass to 300 parts by mass, more preferably 3 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. The range of ~100 parts by mass is further preferably in the range of 5 parts by mass to 45 parts by mass. When the content of the elastomer is within these ranges, it is possible to obtain an effect that is more excellent in ensuring heat resistance and toughness of the molded article.

The crosslinkable resin blended in the composition of the polyarylene sulfide resin has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amine group, a decylamino group, a carboxyl group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

The epoxy resin is preferably an aromatic epoxy resin. The aromatic epoxy resin may have a halogen group or a hydroxyl group. Examples of preferred aromatic epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, and tetramethylbiphenyl. Epoxy resin, phenol novolac type epoxy Resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction Type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-reduced phenolic type epoxy resin, naphthol-A Phenolic co-phenolic varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, and biphenyl aldehyde varnish type epoxy resin. These aromatic epoxy resins may be used singly or in combination of two or more. Among these aromatic epoxy resins, a novolac type epoxy resin is preferable, and a cresol novolak type epoxy resin is more preferable because it is excellent in compatibility with other resin components.

The content of the crosslinkable resin is preferably from 1 part by mass to 300 parts by mass, more preferably from 3 parts by mass to 100 parts by mass, even more preferably 5 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. ~30 parts by mass range. When the content of the crosslinkable resin is within these ranges, the effect of improving the rigidity and heat resistance of the molded article can be particularly remarkably obtained.

The polyarylene sulfide resin composition may contain a decane compound having a functional group reactive with a group represented by the formula (1). Examples of the decane compound include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and β-(3,4-epoxycyclohexyl)ethyltrimethyl. A decane coupling agent such as oxydecane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxydecane.

The content of the decane compound is, for example, relative to the mass of the polyarylene sulfide resin 100 The portion is preferably in the range of 0.01 part by mass to 10 parts by mass, more preferably in the range of 0.1 part by mass to 5 parts by mass. By the content of the decane compound being within these ranges, an effect of improving the compatibility of the polyarylene sulfide resin with the other components can be obtained.

The polyarylene sulfide resin composition of the present embodiment may further contain other additives such as a release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust preventive, a flame retardant, and a lubricant. The content of the additive is, for example, preferably in the range of 1 part by mass to 10 parts by mass based on 100 parts by mass of the polyarylene sulfide resin.

The polyarylene sulfide resin composition can be obtained by melt-kneading the polyarylene sulfide resin obtained by the above method and the other components, for example, in the form of a pellet-like compound. . The temperature of the melt kneading is, for example, preferably in the range of 250 ° C to 350 ° C, and more preferably in the range of 290 ° C to 330 ° C. The melt kneading can be carried out using a twin screw extruder or the like.

The polyarylene sulfide resin composition of the present embodiment may be used alone or in combination with materials such as the other components, and may be subjected to various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding. It is processed into a molded article excellent in heat resistance, moldability, dimensional stability, and the like. Since the polyarylene sulfide resin composition of the present embodiment has a small amount of gas generated during heating, a high-quality molded article can be easily produced.

The polyarylene sulfide resin composition of the present embodiment also has various properties such as heat resistance and dimensional stability which the polyarylene sulfide resin originally has. Therefore, for example, a connector can be obtained by, for example, injection molding and compression molding. ), printed substrate (printing substrate) and sealed molded products and other electrical. Electronic parts, lamp reflection Automotive components such as lamp reflectors and various electrical component parts, interior materials for various buildings, airplanes, and automobiles, office automation (OA) machine parts, camera parts, and timepieces Precision parts such as parts. Further, the polyarylene sulfide resin composition of the present invention can be widely used as various molding materials for extrusion molding, drawing and the like of composites, sheets, pipes, and the like. And materials for fibers or films.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited to the embodiments.

Evaluation method

1-1. Melt viscosity of PPS resin

Using a flow tester CFT-500C manufactured by Shimadzu Corporation, the PPS resin was held at 300 ° C under a load of 1.96 × 10 ⁶ Pa and L/D = 10/1 for 6 minutes, and then the melt viscosity was measured.

1-2. The melting point of PPS resin

Using a DSC manufactured by PerkinElmer, a sample of the PPS resin was heated from 50 ° C to 20 ° C / min to 350 ° C, and the peak temperature of the endothermic peak at the time of melting the polymer was defined as the melting point.

1-3. Iodine content in PPS resin

The Pion resin is burned using a Dionex Instruments combustion gas absorption device, and pure water is used to absorb the generated gas and residue. Use Dion Ion chromatography (Dionex Ion Chromatography) quantifies the iodide ions in the absorbing solution.

1-4. Proportion of disulfide bonds in PPS resin

The total amount of sulfur atoms (total amount of sulfur) was measured using a fluorescent X-ray analyzer ZSX100e manufactured by Rigaku Denki Co., Ltd., and the ratio of the disulfide bonds in the PPS resin was determined based on the following formula.

1-5. Bending characteristics

. Standard Test Method...American Society for Testing and Materials (ASTM) D-790

. Test piece...3.2mm (thickness) × 12.7mm (width) × 127mm (long)

. Test result...the average of the test number n=10

1-6. Charpy impact strength

. Standard Test Method...International Organization For Standardization, ISO) 177-1 (notch/notched)

. Test piece...4.0mm (thickness) × 10.0mm (width) × 100mm (long)

. Test result...the average of the test number n=10

1-7. Acid resistance test / alkali resistance test

The test piece was immersed in the test solution in a state where the test piece was subjected to bending stress so as to have a predetermined bending strain, and the time until the test piece was broken was investigated. Test A cutting recess is provided at the center of the sheet.

. Acid resistance test solution...Sunpole stock solution (trade name, surfactant containing hydrochloric acid and surfactant, manufactured by Dainiper)

. Alkali resistance test solution...Domesto stock solution (trade name, alkaline lotion containing sodium hypochlorite, sodium hydroxide and surfactant, manufactured by Nippon Lever)

. Test piece...1.6mm (thickness) × 12.7mm (width) × 127mm (long)

. Bending strain...1.2% (the bending stress in the test method for bending characteristics specified in ASTM D-790 is loaded on the test piece)

. Evaluation item... until the test piece breaks

. Test result...the average of the test number n=5

1-8. Hot water resistance test

The test piece was immersed in hot water at 95 ° C, and the change in bending strength with time was investigated.

. Test piece...3.2mm (thickness) × 12.7mm (width) × 127mm (long)

. Test method for bending strength...ASTM D-790

. Evaluation item...Preservation rate of bending strength after 1000 hours and 3000 hours with respect to initial strength

. Test result...the average of the test number n=5

1-9. Cavity balance

Using a washer mold having 40 cavities, the PPS composite was injection molded under the lowest forming conditions in a range in which the cavity (C1) closest to the primary sprue was completely filled. The forming conditions are set to 75 tons. The temperature of the machine and the cylinder is 320 ° C, the mold temperature is 140 ° C, and there is no holding pressure.

The degree of filling of the molded cavity (C10) which is located at the same runner as the cavity (C1) and which is farthest from the primary runner is compared. The degree of filling (% by mass) is determined from the mass ratio of the molded article of the cavity (C10) to the molded article of the cavity (C1). It can be said that the higher the filling degree of the cavity (C10), the more excellent the cavity balance. The cavity balance of each composition was determined based on the degree of filling and according to the following criteria.

AA: range of 100% by mass to 90% by mass

A: range of 89% by mass to 80% by mass

B: range of 79% by mass to 70% by mass

C: range of 69% by mass to 60% by mass

D: range below 59% by mass

1-10. The amount of gas produced

A predetermined amount of the sample of the polyarylene sulfide resin or the resin composition was heated at 325 ° C for 15 minutes using a gas chromatography mass spectrometry apparatus, and the amount of generated gas at this time was quantified by mass%.

2. Synthesis of polyphenylene sulfide resin (PPS resin) (Table 1)

(Synthesis Example 1)

50% of p-diiodobenzene (Tokyo Chemical Co., Ltd., p-diiodobenzene purity 98.0% or more), solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) 27.00 g, 4,4'-dithio Dibenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobisbenzoic acid, technical grade) 2.0 g was heated to 180 ° C under a nitrogen atmosphere, and these were dissolved and mixed. . Second, heat up to 220 ° C, Reduce the pressure to an absolute pressure of 26.6 kPa. The obtained molten mixture was heated stepwise by changing the temperature and pressure so as to be 320 ° C in the system and an absolute pressure of 133 Pa, and the melt polymerization was carried out for 8 hours. After completion of the reaction, 200 g of NMP was added, and the mixture was heated and stirred at 220 ° C, and the obtained dissolved matter was filtered. 320 g of NMP was added to the filtered lysate, and the cake was washed and filtered. To the obtained NMP-containing filter cake, 1 L of ion-exchanged water was added, and the mixture was stirred at 200 ° C for 10 minutes in an autoclave. Then, the cake was filtered, and 1 L of ion-exchange water at 70 ° C was added to the filtered cake to carry out filter cake washing. To the obtained aqueous filter cake, 1 L of ion-exchanged water was added and stirred for 10 minutes. Then, the cake was filtered, and 1 L of ion-exchange water at 70 ° C was added to the filtered cake to carry out filter cake washing. After repeating this operation again, the cake was dried at 120 ° C for 4 hours to obtain 91 g of a PPS resin. The obtained PPS resin had an iodine content of 200 ppm and a disulfide bond ratio of 0.2% by mass.

(Synthesis Example 2)

91 g of a PPS resin was obtained in the same manner as in Synthesis Example 1, except that "2-iodoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)" was used instead of the "4,4'-dithiobisbenzoic acid".

(Synthesis Example 3)

PPS resin was obtained in the same manner as in Synthesis Example 1, except that "diphenyl disulfide (Sumitomo Chemical Co., Ltd. DPDS)" was used instead of the "4,4'-dithiobisbenzoic acid". 91g.

(Synthesis Example 4)

600 g of N-methylpyrrolidone (hereinafter abbreviated as NMP) and 336.3 g (2.0 mol) of sodium sulfide pentahydrate were added to the autoclave, and the temperature was raised to 200 ° C under a nitrogen atmosphere, thereby distilling the water-NMP mixture. Remove. Then, a solution obtained by dissolving 292.53 g of p-dichlorobenzene and 1.62 g of 2,5-dichloroaniline in 230 g of NMP was added to the system, and the reaction was carried out at 220 ° C for 5 hours under nitrogen atmosphere, and further reacted at 240 ° C. 2 hours. After cooling the reaction vessel, the contents were extracted, a portion was sampled, and unreacted 2,5-dichloroaniline was quantified by a gas chromatograph. Further, the remaining slurry was washed several times with hot water, and the polymer cake was separated by filtration. The cake was dried under reduced pressure at 80 ° C to obtain a powdery PPS resin. The infrared absorption spectrum was measured, and as a result, an absorption spectrum which can be regarded as an amine group was observed in the vicinity of 3380 cm ^-1 .

3. Polyphenylene sulfide resin composition (PPS composite)

3-1. Raw materials

The following materials were prepared in order to prepare a PPS resin composition.

(thermoplastic elastomer)

. ELA: copolymer of ethylene/glycidyl methacrylic acid (3 mass%) / methyl acrylate (27 mass%) (manufactured by Sumitomo Chemical Industries, Ltd., "Bondfast 7L")

(thermoplastic resin)

. PA6T: aromatic polydecylamine obtained by reacting 65 mol% of terephthalic acid, 25 mol% of isophthalic acid, and 10 mol% of adipic acid as essential monomer components (melting point 310 ° C, Tg 120 °C)

. PA9T: Polydecylamine obtained by reacting decane diamine with terephthalic acid (manufactured by Kuraray Co., Ltd., "Genestar N1000A")

. PA46: Polyamide 46 (manufactured by DSM Japan Engineering Plastics Co., Ltd., "Stanyl TS300")

. PPE: poly(2,6-dimethyl-1,4-phenylene) ether (intrinsic viscosity 0.45 dl/g (30 ° C, in chloroform))

. PES: Aromatic polyfluorene resin (manufactured by Sumitomo Chemical Industries, Ltd., product name: Sumika Excel PES4100P)

. PAR: aromatic polyester synthesized by the following method

3,3',5,5'-tetramethyl-1,1'-biphenyl-4,4'-diol 2.42 Kg (10.0 mol) in a polymerization apparatus equipped with a stirring blade and a nitrogen inlet 50 g of m-cresol was dissolved in 30 L of deoxygenated water containing 1.0 kg of sodium hydroxide to obtain an aqueous solution. In addition, 64 g of tetrabutylammonium bromide, m-xylylene chloride 1.62 Kg (8.0 mol), and terephthalic acid chloride 0.41 Kg (2.0 mol) were dissolved in 5 L of dichloromethane to obtain an organic solution. . The organic solution was added while stirring the aqueous solution under a nitrogen gas stream, and stirring was continued at 25 ° C for 30 minutes, and then the aqueous phase was removed. The organic solution phase containing the product was repeatedly washed with distilled water, poured into an acetone bath to obtain a precipitate, and further washed with acetone to obtain an aromatic polyester. Thereafter, vacuum drying was carried out by vacuum drying at 200 ° C under a reduced pressure of about 10 Pa for 3 hours to obtain 3.2 kg of an aromatic polyester.

. LCP: a thermotropic liquid crystal polyester resin synthesized by the following method

55.1 g (0.5 mol) of hydroquinone, 93.1 g (0.5 mol) of 4,4'-dihydroxybiphenyl, 116.3 g (0.7 mol) of terephthalic acid, and 24.9-dicarboxynaphthalene 64.9 g (0.3 mol), 621.5 g (4.5 mol) of p-hydroxybenzoic acid, and 612.5 g (6 mol) of acetic anhydride were added to a reaction vessel equipped with a cooler and a stirrer, and the mixture was heated while stirring under a nitrogen atmosphere. It was refluxed at 170 ° C for 60 minutes. Then, while removing acetic acid as a by-product, the reaction vessel was slowly raised for 4 hours. The reaction system was reduced to 25 kPa at 370 ° C to 370 ° C. Further, at this temperature, acetic acid as a by-product was removed, and the pressure was reduced to 0.5 kPa to 1 kPa for 2 hours to carry out polymerization. Then, polymerization was carried out at 370 ° C for 1 hour. While the by-produced acetic acid was removed, polymerization was carried out under vigorous stirring, and thereafter, the system was slowly cooled, and the liquid crystal polyester resin obtained at 200 ° C was extracted out of the system.

(decane coupling agent)

. Epoxy decane: γ-glycidoxypropyltrimethoxydecane

(crosslinkable resin)

. Epoxy resin: cresol novolak type epoxy resin (Dainippon Ink and Chemicals, DIC), "Epiclon N-695", epoxy equivalent 214g / eq, softening point 94 °C)

(Inorganic filler)

. GF: glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

. CF: pitch-based carbon fiber, tensile modulus 560GPa

. Carbon black: graphitized carbon black

. CaCO ₃ (calcium carbonate): manufactured by Marui Co., Ltd., "Caltex 5" (powder, average particle size 1.2 μm)

3-2. Fabrication and evaluation of composites

The raw materials were uniformly mixed using a tumbler using the composition shown in Tables 2 to 6, and then a biaxial kneading extruder (TEM-35B, Toshiba Machine) was used at 300 ° C. Melt kneading is carried out to obtain a granulated composite. The obtained composite was injection-molded at a cylinder temperature of 300 ° C and a mold temperature of 140 ° C to prepare for bending properties, Izod impact strength, acid resistance test, alkali resistance test or heat resistance. The test piece of the water-based test was subjected to various evaluations. Further, the amount of generated gas was measured for the PPS resin alone and the composite. The evaluation results are shown in the respective tables.

As is clear from the results shown in the respective tables, the amount of generated gas of the resin composition obtained by blending the PPS resin of the synthesis example 1 with the inorganic filler and various resins, and the synthesis example 2 and the synthesis example by melt polymerization were confirmed. 3 is significantly lower than the comparison. Further, the resin composition obtained by using the PPS resin of Synthesis Example 1 is also excellent in mechanical properties (bending, impact), acid resistance, alkali resistance, hot water resistance, and cavity balance.

Claims (3)

A polyarylene sulfide resin composition comprising a polyarylene sulfide resin and a thermoplastic resin selected from the group consisting of inorganic fillers, polyarylene sulfide resins, elastomers, and having two or more crosslinkable functional groups At least one other component of the group consisting of a crosslinkable resin, and the polyarylene sulfide resin can be represented by including a diiodide aromatic compound, elemental sulfur, and having the following formula (1) The polymerization inhibitor of the group is obtained by a method comprising the step of reacting in the molten mixture of the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor: (wherein X represents a hydrogen atom or an alkali metal atom). The polyarylene sulfide resin composition according to the first aspect of the invention, wherein the polymerization inhibitor comprises a compound represented by the following formula (2), a compound represented by the following formula (3), or A compound represented by the following formula (4): In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent group represented by the following formula (a), a monovalent group represented by the following formula (b), or the following a monovalent group represented by the formula (c), and at least one of R ¹ or R ² is represented by the formula (a), the formula (b) or the formula (c) Monovalent group, (wherein X represents a hydrogen atom or an alkali metal atom) (wherein R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms) (wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms)] (wherein Z represents an iodine atom or a fluorenyl group, and R ³ represents a monovalent value represented by the above formula (a), the formula (b) or the formula (c)) (wherein R ⁴ represents the monovalent group represented by the above formula (a), the formula (b) or the formula (c)). A molded article obtained by molding a polyarylene sulfide resin composition as described in claim 1 or 2.