KR102570299B1 - Polyarylene sulfide resin composition and molded product thereof, and surface-mount electronic component - Google Patents

Abstract

A polyarylene sulfide resin composition capable of suppressing the amount of gas generated by heating and having excellent properties in a resin composition or a molded product thereof, a molded product using the resin composition, and an electronic component provided with the molded product. Specifically, at least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition for surface-mounted electronic components containing, wherein the polyarylene sulfide resin comprises a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor, a diiodo aromatic compound, simple sulfur and polymerization A polyarylene sulfide resin composition for surface-mounted electronic parts obtained by a method including reacting in a molten mixture containing an inhibitor, a molded article using the resin composition, and an electronic part provided with the molded article.

Description

Polyarylene sulfide resin composition, molded product thereof, and surface mounted electronic component

The present invention relates to a polyarylene sulfide resin composition, a molded product thereof, and a surface-mounted electronic component.

In recent years, in the field of electrical/electronic industry, with the miniaturization of products and the improvement of productivity, the method of mounting resin-based electronic components on printed circuit boards is called the surface mount method (hereinafter sometimes abbreviated as “SMT method”). It is moving to the so-called surface mounting method. Conventionally, tin-lead eutectic solder (melting point: 184°C) has been common in the technology of mounting electronic components on a board by this SMT method, but in recent years, due to the problem of environmental pollution, tin has been used as an alternative material. Lead-free solder with several types of metal added as a base is used.

Such lead-free solder has a higher melting point than tin-lead eutectic solder. For example, in the case of tin-silver eutectic solder, the melting point reaches 220 ° C. I had to raise it higher. Therefore, when soldering resin-based electronic components such as connectors, there has been a problem that the electronic component melts or deforms in a heating furnace (reflow furnace). Therefore, resin materials used for surface-mounted electronic parts have been strongly required to have high heat resistance.

On the other hand, polyarylene sulfide resin (hereinafter sometimes abbreviated as "PAS resin") typified by polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PPS resin") is used as a resin material having high heat resistance. It has been proposed to use, a molded article of a resin composition containing the polyarylene sulfide resin and a surface-mounted electronic component provided with a metal terminal suppresses melting or deformation of the electronic component even in a heating furnace (reflow furnace). What can be done has been proposed (see Patent Document 1, for example).

International Publication No. 2009/096401

However, in a composition containing a conventional polyarylene sulfide resin, the amount of gas generated by heating during molding processing or the like is relatively large, and there is a concern that metal terminals of electronic parts may be corroded. Further, in conventional polyarylene sulfide resin compositions or molded products thereof, there is still room for improvement in properties such as mechanical strength, metal adhesion, and cavity balance.

Then, the problem to be solved by the present invention is that the amount of gas generated by heating can be suppressed while preventing melting or deformation of surface-mounted electronic components in a heating furnace (reflow furnace), and furthermore, a resin composition Or, in the molded article, a polyarylene sulfide resin composition having excellent mechanical strength, metal adhesion, and cavity balance characteristics, a molded article using the resin composition, and a surface-mounted electronic component provided with the molded article.

As a result of various studies, the inventors of the present invention have found that the above problems can be solved by using a polyarylene sulfide resin having a specific functional group at the terminal, and have completed the present invention.

That is, the present invention is at least one selected from the group consisting of polyarylene sulfide resin, inorganic filler, thermoplastic resin other than polyarylene sulfide resin, elastomer, and crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition for surface-mounted electronic components containing other components, wherein the polyarylene sulfide resin comprises a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor. , It relates to a polyarylene sulfide resin composition for surface-mounted electronic components, which can be obtained by a method comprising reacting in a molten mixture containing a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor.

According to the present invention, it is possible to suppress the amount of gas generated by heating while preventing melting or deformation of surface-mounted electronic components in a heating furnace (reflow furnace), and furthermore, in a resin composition or a molded product thereof, It is an object of the present invention to provide a polyarylene sulfide resin composition having excellent mechanical strength, metal adhesion, and cavity balance characteristics, a molded product using the resin composition, and a surface-mounted electronic component provided with the molded product.

In addition, the cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded products are simultaneously molded by injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is not sufficient, molding defects in which some cavities are not sufficiently filled tend to occur easily.

EMBODIMENT OF THE INVENTION Hereinafter, suitable embodiment of this invention is described in detail. However, this invention is not limited to the following embodiment.

The polyarylene sulfide resin used in the present embodiment is to react a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing a diiodoaromatic compound, elemental sulfur, and a polymerization inhibitor. can be obtained by including According to this method, a polyarylene sulfide resin can be obtained as a relatively high molecular weight polymer compared to conventional methods such as the Phillips method.

A diiodo aromatic compound has an aromatic ring and two iodine atoms bonded directly to the aromatic ring. As diiodo aromatic compounds, diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododi Phenylsulfone etc. are mentioned, but it is not limited to these. The substitution sites of the two iodine atoms are not particularly limited, but it is preferable that the two substitution sites are located as far apart as possible in the molecule. Preferred substitution positions are the para position and the 4,4'- position.

The aromatic ring of the diiodo aromatic compound is at least one selected from a phenyl group, a halogen atom other than an iodine atom, a hydroxyl group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone, and an arylketone. It may be substituted by the substituent of the species. However, from the viewpoint of the crystallinity and heat resistance of the polyarylene sulfide resin, the ratio of the substituted diiodo aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001 to 5% by mass, and more Preferably it is the range of 0.001-1 mass %.

Elementary sulfur means a substance (S ₈ , S ₆ , S ₄ , S _{2 ,} etc.) composed only of sulfur atoms, and its form is not limited. Specifically, commercially available elemental sulfur may be used as a national defense medicine, or a mixture containing S ₈ and S ₆ that is generally available may be used. The purity of elemental sulfur is not particularly limited either. Elementary sulfur may be granular or powdery as long as it is solid at room temperature (23°C). The particle size of elemental sulfur is not particularly limited, but is preferably in the range of 0.001 to 10 mm, more preferably in the range of 0.01 to 5 mm, still more preferably in the range of 0.01 to 3 mm.

As the polymerization inhibitor, in the polymerization reaction of polyarylene sulfide resin, any compound that inhibits or stops the polymerization reaction can be used without particular limitation. The polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxy group, and a salt of a carboxy group at the terminal of the main chain of the polyarylene sulfide resin. That is, as the polymerization inhibitor, a compound having one or two or more groups of at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and a salt of a carboxy group is preferable. In addition, the polymerization inhibitor may have the above functional group, or may generate the above functional group by a polymerization termination reaction or the like.

As the polymerization inhibitor having a hydroxy group or an amino group, for example, a compound represented by the following formula (1) or (2) can be used as the polymerization inhibitor.

According to the compound represented by the general formula (1), a monovalent group represented by the following formula (1-1) is introduced as an end group of the main chain. Y in formula (1-1) is a hydroxyl group derived from a polymerization inhibitor, an amino group, etc.

According to the compound represented by the general formula (2), a monovalent group represented by the following formula (2-1) is introduced as an end group of the main chain. A hydroxy group derived from the compound represented by the general formula (1) can be introduced into the polyarylene sulfide resin by, for example, bonding with a carbon atom of the carbonyl group in the formula (2) and a sulfur radical.

The group represented by formula (1-1) or (2-1) is a sulfur generated by radical cleavage of a disulfide bond derived from a raw material (single element sulfur) and present in the main chain of polyarylene sulfide resin at a melting temperature. It is considered that the radical is introduced into the polyarylene sulfide resin by bonding the compound represented by the general formula (1) or the compound represented by the general formula (2). The presence of these structural units of specific structure is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the general formula (1) or (2).

As a compound represented by General formula (1), 2-iodophenol, 2-aminoaniline, etc. are mentioned, for example. As a compound represented by General formula (2), 2-iodo benzophenone is mentioned.

As the polymerization inhibitor having a carboxy group, one or more compounds selected from compounds represented by the following general formulas (3), (4) or (5) can be used, for example.

In formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following formula (a), (b) or (c), and among R ¹ or R ² At least one of them is a monovalent group represented by general formula (a), (b) or (c). In general formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent group represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ represents a monovalent group represented by general formula (a), (b) or (c).

X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom, but a hydrogen atom is preferable in terms of good reactivity. Although sodium, lithium, potassium, rubidium, and cesium etc. are mentioned as an alkali metal atom, sodium is preferable. In general formula (b), R ¹⁰ represents an alkylene group having 1 to 6 carbon atoms. In formula (c), R ¹¹ represents an alkylene group having 1 to 3 carbon atoms; R ¹² represents an alkyl group having 1 to 5 carbon atoms.

According to the compound represented by general formula (3), (4) or (5), a monovalent group represented by the following formula (6) or (7) is introduced as an end group of the main chain. The presence of the terminal structural unit of these specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by General formula (3), (4) or (5).

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

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

As a polymerization inhibitor, you may use the compound etc. which do not have functional groups, such as a carboxy group. Examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, and N-cyclohexyl-2-benzothia. At least one compound selected from zolyl sulfenamide, 2-(morpholinothio)benzothiazole, and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.

The polyarylene sulfide resin according to the present embodiment is produced by performing melt polymerization in a molten mixture obtained by heating a mixture containing a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and, if necessary, a catalyst. do. The ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 moles, more preferably in the range of 0.8 to 1.2 moles, relative to 1 mole of elemental sulfur. The ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mole, more preferably in the range of 0.0005 to 0.05 mole, per mole of solid sulfur.

The timing for adding the polymerization inhibitor is not particularly limited, but a mixture containing a diiodo aromatic compound, elemental sulfur, and a catalyst added as needed is heated, and the temperature of the mixture is preferably 200°C to 320°C. A polymerization inhibitor can be added at the time of reaching the range, more preferably within the range of 250 to 320°C.

The rate of polymerization can be controlled by adding a nitro compound as a catalyst to the molten mixture. As this nitro compound, various nitrobenzene derivatives can be used normally. As the nitrobenzene derivative, for example, 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diio Do-4-nitroamine is mentioned. The amount of the catalyst may normally be any amount added as a catalyst, and for example, it is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur.

Conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably in the range of 175°C or higher, the melting point of the polyarylene sulfide resin to be produced +100°C or lower, and more preferably in the range of 180 to 350°C. Melt polymerization is carried out at an absolute pressure preferably in the range of 1 [cPa] to 100 [kPa], more preferably in the range of 13 [cPa] to 60 [kPa]. The conditions for melt polymerization do not need to be constant. For example, in the initial stage of polymerization, the temperature is preferably in the range of 175 to 270 ° C., more preferably in the range of 180 to 250 ° C., and the absolute pressure is in the range of 6.7 to 100 [kPa]. After that, Polymerization is carried out while raising and reducing the temperature continuously or stepwise, and in the latter stage of the polymerization, the temperature is preferably 270 ° C. or higher, the melting point of the polyarylene sulfide resin to be produced + 100 ° C. or lower, more preferably 300 to 350 ° C. Polymerization can be carried out within the range of °C and absolute pressure within the range of 1 [cPa] to 6 [kPa]. In this specification, the melting|fusing point of resin means the value measured based on JISK7121 using a differential scanning calorimeter (DSC device Pyris Diamond by Perkin Elmer).

From the viewpoint of obtaining a high degree of polymerization while preventing an oxidative crosslinking reaction, the melt polymerization is preferably performed in a non-oxidizing atmosphere. In a non-oxidizing atmosphere, the oxygen concentration of the gas phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, still more preferably the gaseous phase contains substantially no oxygen. . The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium, and argon.

Melt polymerization can be performed, for example, using a melt kneading machine equipped with a heating device, a pressure reducing device, and a stirring device. As a melt kneading machine, a Banbury mixer, a kneader, a continuous kneading machine, a single screw extruder, and a twin screw extruder are mentioned, for example.

It is preferable that the melt mixture for melt polymerization contains substantially no solvent. More specifically, the amount of the solvent contained in the molten mixture is preferably 10 parts by mass relative to 100 parts by mass in total of the diiodo aromatic compound, elemental sulfur, polymerization inhibitor, and, if necessary, the catalyst. It is within the following ranges, more preferably within the range of 5 parts by mass or less, and even more preferably within the range of 1 part by mass or less. The amount of the solvent may be in the range of 0 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more.

After cooling the molten mixture (reaction product) after melt polymerization to obtain a solid mixture, the mixture may be heated under reduced pressure or under atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. In this way, not only can the molecular weight be further increased, but also the iodine atom concentration in the polyarylene sulfide resin can be suppressed to a low level because the generated iodine molecules are sublimated and removed. A mixture in a solid state can be obtained by cooling to a temperature preferably in the range of 100 to 260°C, more preferably in the range of 130 to 250°C, and still more preferably in the range of 150 to 230°C. Heating after cooling to a solid state can be performed under the same temperature and pressure conditions as in melt polymerization.

The reaction product containing the polyarylene sulfide resin obtained in the melt polymerization step may be directly introduced as it is into a melt kneader or the like to prepare a resin composition, but the reaction product is dissolved in a solvent in which the reaction product is dissolved. It is preferable to prepare a melt by adding and take out the reaction product from the reaction device in the state of the melt because not only productivity is excellent but also the reactivity is further improved. The addition of the solvent in which the reaction product is dissolved is preferably performed after melt polymerization, but may be performed later in the reaction of melt polymerization. Further, as described above, the molten mixture (reaction product) is cooled to obtain a solid-state mixture. After that, the mixture may be heated to further advance the polymerization reaction under increased pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere. You may perform the process of preparing the said melt|dissolution in a non-oxidizing atmosphere. In addition, the melting temperature by heating should just be in the range equal to or higher than the melting point of the solvent in which the reaction product is dissolved, and is preferably in the range of 200 to 350°C, more preferably in the range of 210 to 250°C, and is preferably performed under pressure. .

The blending ratio of the solvent in which the reaction product is dissolved, used to prepare the melt, is preferably in the range of 90 to 1000 parts by mass, more preferably in the range of 90 to 1000 parts by mass, relative to 100 parts by mass of the reaction product containing the polyarylene sulfide resin. It is in the range of 200 to 400 parts by mass.

As the solvent in which the reaction product dissolves, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as the Phillips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazoli. Aliphatic cyclic amide compounds such as dinonic acid, ε-caprolactam, N-methyl-ε-caprolactam, hexamethylphosphatetriamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide amide compounds such as (DMA), etherified polyethylene glycol compounds such as polyethylene glycol dialkyl ether (having a degree of polymerization of 2000 or less and having an alkyl group of 1 to 20 carbon atoms), and tetramethylene sulfoxide and dimethyl sulfoxide and sulfoxide compounds such as seed (DMSO). Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4'-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxa Diazole, 2,5-diphenyloxazole, triphenylmethanol, N,N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, Pentachlorophenol, 1-benzyl-2-pyrrolidione, 9-fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrroly Dinon, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o,o '-biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thianthrene, 3-phenoxybenzyl alcohol, 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4, 4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenylphthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromodi Phenyl ether, pyrene, 9,9'-bi-fluorene, 4,4'-isopropylidene-diphenol, ε-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenylisophthalate, diphenyl and at least one solvent selected from the group consisting of terephthalate and 1-chloronaphthalene.

After performing a post-processing of the said melt|dissolution taken out from the reaction apparatus, it is preferable to melt-knead with the said other component and prepare a resin composition since reactivity becomes more favorable. The post-processing method of the lysate is not particularly limited, and examples thereof include the following methods.

(1) The lysate as it is or after adding an acid or base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid material after the solvent is distilled off is water, the solvent used for the lysate (or a low molecular weight polymer organic solvents having equivalent solubility to water), acetone, methyl ethyl ketone, alcohols, etc., washing once or twice or more, and further neutralizing, washing with water, filtering, and drying.

(2) Solvents such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons in the melt (soluble in the solvent of the melt, and at least polyarylene sulfide) A method of precipitating a solid product containing a polyarylene sulfide resin and an inorganic salt by adding a solvent which is a poor solvent to the resin as a precipitating agent, and filtering, washing, and drying the solid product.

(3) To the lysate, the solvent used in the lysate (or an organic solvent having equivalent solubility to the low molecular weight polymer) is added and stirred, followed by filtration to remove the low molecular weight polymer, followed by water, acetone, methyl ethyl ketone and A method of washing once or twice or more with a solvent selected from alcohol and the like, followed by neutralization, washing with water, filtration and drying.

Further, in the post-treatment methods as exemplified in (1) to (3) above, drying of the polyarylene sulfide resin may be performed in a vacuum, or may be performed in air or in an inert gas atmosphere such as nitrogen. The polyarylene sulfide resin may be oxidatively crosslinked by performing heat treatment in an oxidizing atmosphere with an oxygen concentration in the range of 5 to 30% by volume or under reduced pressure conditions.

The reaction which polyarylene sulfide resin produces by melt polymerization is illustrated below.

Reaction formulas (1) to (5) are, for example, when diphenyldisulfide having a substituent R containing a group represented by general formula (a), (b) or (c) is used as a polymerization inhibitor, This is an example of a reaction that polyphenylene sulfide produces. Reaction formula (1) is a reaction in which the -S-S- bond in the polymerization inhibitor is radically cleaved under the melting temperature. In Reaction Formula (2), the sulfur radical generated in Reaction Formula (1) attacks the carbon atom adjacent to the iodine atom at the terminal of the growing main chain, and the iodine atom is released, thereby stopping the polymerization and introducing a substituent R at the terminal of the main chain. is a reaction Reaction formula (3) is a reaction in which a disulfide bond derived from a raw material (single element sulfur) and present in the main chain of polyarylene sulfide resin is radically cleaved under the melting temperature. Reaction formula (4) is a reaction in which a substituent R is introduced to the terminal of the main chain while polymerization is stopped by recombination of sulfur radicals generated in reaction formula (3) with sulfur radicals generated in reaction formula (1). Iodine molecules are generated when the iodine atoms that have escaped are in a free state (iodine radicals) or when iodine radicals recombine with each other as shown in Reaction Formula (5).

A reaction product containing polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from raw materials. Therefore, polyarylene sulfide resin is usually used in the state of a mixture containing an iodine atom for preparation of a resin composition for spinning and the like. The concentration of iodine atoms in the mixture is, for example, in the range of 0.01 to 10000 ppm with respect to the polyarylene sulfide resin, and preferably in the range of 10 to 5000 ppm. Utilizing the sublimation properties of iodine molecules, it is also possible to suppress the iodine atom concentration to a low level. In that case, it is also possible to set it as 900 ppm or less, preferably 100 ppm or less, and also 10 ppm or less. Although it is possible to further remove iodine atoms below the detection limit, it is not practical considering productivity. The detection limit is, for example, about 0.01 ppm. Since the polyarylene sulfide resin of the present embodiment obtained by melt polymerization or a reaction product containing the same contains an iodine atom, for example, solution polymerization of a dichloroaromatic compound in an organic polar solvent such as the Phillips method It can be clearly distinguished from polyarylene sulfide obtained by the method.

As can be understood from the above reaction formula, the polyarylene sulfide resin obtained by melt polymerization comprises a main chain mainly composed of an arylene sulfide unit composed of an aromatic ring derived from a diiodo aromatic compound and a sulfur atom directly bonded thereto; It contains a predetermined substituent R bonded to the terminal of the main chain. The predetermined substituent R is bonded to the aromatic ring at the terminal of the main chain directly or through a partial structure derived from a polymerization inhibitor.

Polyphenylene sulfide resin as a polyarylene sulfide resin according to one embodiment, for example, the following general formula (10):

It has a main chain including a repeating unit (arylene sulfide unit) represented by The repeating unit represented by formula (10) is bonded at the para-position by the following formula (10a):

A repeating unit represented by , and the following formula (10b) bonded at a meta position:

It is more preferably a repeating unit represented by . Among these, the repeating unit bonded at the para position represented by formula (10a) is preferable from the viewpoint of heat resistance and crystallinity of the resin.

The polyphenylene sulfide resin according to one embodiment has the following general formula (11):

(In the formula, R ²⁰ and R ²¹ each independently represent 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), bonded to an aromatic ring A repeating unit having a substituent as a side chain may be included. However, it is preferable that the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11) from the viewpoint of the decrease in crystallinity and heat resistance. More specifically, the ratio of the repeating unit represented by formula (11) is preferably 2% by mass or less relative to the total of the repeating unit represented by formula (10) and the repeating unit represented by formula (11). , More preferably, it is 0.2 mass % or less.

The polyarylene sulfide resin of the present embodiment is mainly composed of the above-mentioned arylene sulfide unit, but is usually derived from simple element sulfur of the raw material, and the following formula (20):

A structural unit based on a disulfide bond represented by is also included in the main chain. From the viewpoint of heat resistance and mechanical strength, the ratio of the structural units represented by formula (20) is preferably 2.9% by mass or less relative to the total of the arylene sulfide units and constituent parts represented by formula (20). range, more preferably 1.2% by mass or less. When the polyarylene sulfide resin contains the structural unit represented by formula (20), it is preferable from the viewpoint of improving the adhesion between the polyarylene sulfide resin composition and the metal.

The Mw/Mtop of the polyarylene sulfide resin according to the present embodiment is preferably in the range of 0.80 to 1.70, more preferably in the range of 0.90 to 1.30. By making Mw/Mtop into such a range, the processability of polyarylene sulfide resin can be improved, and favorable cavity balance can be provided. In the present specification, Mw represents the weight average molecular weight measured by gel permeation chromatography, and Mtop represents the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram obtained by the same measurement becomes maximum. Mw/Mtop represents the molecular weight distribution of the object to be measured, and usually, when this value is close to 1, the molecular weight distribution is narrow, and as this value increases, the molecular weight distribution is wide. In addition, the measurement conditions of the gel permeation chromatography are the same as those in the Examples of the present specification. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw/Mtop.

The weight average molecular weight of the polyarylene sulfide resin according to the present embodiment is not particularly limited as long as the effect of the present invention is not impaired, but the lower limit thereof is preferably 28,000 or more in view of excellent mechanical strength, and is in the range of 30,000 or more it is more preferable On the other hand, the upper limit is preferably in the range of 100,000 or less, more preferably in the range of 60,000 or less, and further preferably in the range of 55,000 or less from the point of being able to provide better cavity balance. Further, from the viewpoint of being excellent in mechanical strength and providing good cavity balance, a polyarylene sulfide resin in the range of 28,000 to 60,000, more preferably a polyarylene sulfide resin in the range of 30,000 to 55,000 In addition, you may use polyarylene sulfide resin in the range of more than 60,000 and 100,000 or less of weight average molecular weight.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, more preferably in the range of 1.0 to 1.70. By setting the non-Newtonian index within this range, the processability of polyarylene sulfide resin can be improved, and good cavity balance can be provided. In this specification, the non-Newtonian index refers to an index that satisfies the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300°C. The non-Newtonian index can be an indicator for the molecular weight of the object to be measured or the molecular structure such as linear chain, branching, or cross-linking. Usually, when this value is close to 1, the molecular structure of the resin is linear, As this value increases, it indicates that a large number of branching and cross-linked structures are included.

D=α× ^Sn

(In the above formula, D represents the shear rate, S represents the shear stress, α represents a constant, and n represents a non-Newtonian exponent)

The polyarylene sulfide resin having Mw / Mtop and non-Newtonian index in the above-described specific range, for example, a diiodo aromatic compound, a simple sulfur, and a polymerization inhibitor, a diiodo aromatic compound, a simple sulfur and a polymerization inhibitor, in a method of reacting (solution polymerization) in a molten mixture containing such polyarylene sulfide resin, it is possible to obtain it by making the polyarylene sulfide resin high in molecular weight to some extent.

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

The polyarylene sulfide resin composition according to the present embodiment may contain one or more inorganic fillers. By blending the inorganic filler, a composition having high rigidity and high heat resistance stability is obtained. Examples of inorganic fillers include powdery fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate-like fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, glass fibers, fibrous fillers such as carbon fibers and wollastonite fibers, and glass flakes. The polyarylene sulfide resin composition preferably contains 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 in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, still more preferably in the range of 15 to 150 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. am. When the content of the inorganic filler is within this range, a more excellent effect is obtained in terms of maintaining the mechanical strength of the molded product.

The polyarylene sulfide resin composition according to the present embodiment may contain a resin other than the polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins. These resins can also be blended in a resin composition together with an inorganic filler.

As the thermoplastic resin blended in the polyarylene sulfide resin composition, for example, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyether ether ketone, polyether ketone, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymers (such as liquid crystal polyester).

Polyamide is a polymer having an amide bond (-NHCO-). Examples of the polyamide resin include (i) a polymer obtained from polycondensation of diamine and dicarboxylic acid, (ii) a polymer obtained from polycondensation of aminocarboxylic acid, and (iii) a polymer obtained from ring-opening polymerization of lactam. there is. Polyamide can be used individually or in combination of 2 or more types.

Examples of the diamine for obtaining polyamide include aliphatic diamine, aromatic diamine, and alicyclic diamine. As the aliphatic diamine, a linear or branched diamine having 3 to 18 carbon atoms is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1, 8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanemethylenediamine, 1,12-dodecamethylenediamine , 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18- octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. These can be used individually or in combination of 2 or more types.

As aromatic type diamine, C6-C27 diamine which has a phenylene group is preferable. Examples of suitable aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodi Phenylsulfide, 4,4'-di(m-aminophenoxy)diphenylsulfone, 4,4'-di(p-aminophenoxy)diphenylsulfone, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(4-aminophenyl)propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis(4-aminophenone cy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino Phenoxy)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 can be heard

These can be used individually or in combination of 2 or more types.

As the alicyclic diamine, diamine having 4 to 15 carbon atoms having a cyclohexylene group is preferable. Examples of suitable alicyclic diamines include 4,4'-diamino-dicyclohexylene methane, 4,4'-diamino-dicyclohexylene propane, and 4,4'-diamino-3,3'-dimethyl. -dicyclohexylenemethane, 1,4-diaminocyclohexane, and piperazine. These can be used individually or in combination of 2 or more types.

Examples of the dicarboxylic acids for obtaining polyamide include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

As the aliphatic dicarboxylic acid, a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable. Examples of suitable aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, and tetradecane. diacid, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can be used individually or in combination of 2 or more types.

As an aromatic dicarboxylic acid, a C8-C15 dicarboxylic acid which has a phenylene group is preferable. Examples of suitable aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and diphenylmethane-4,4'-dicarboxylic acid. , diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid can be heard These can be used individually or in combination of 2 or more types. In addition, polyhydric carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can also be used within a range capable of melt molding.

As aminocarboxylic acid, C4-C18 aminocarboxylic acid is preferable. Examples of suitable aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12- aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These can be used individually or in combination of 2 or more types.

As a lactam for obtaining polyamide, ε-caprolactam, ω-laurolactam, ζ-enantholactam, and η-capryllactam are mentioned, for example. These can be used individually or in combination of 2 or more types.

Preferable combinations of raw materials for polyamide include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine/adipic acid (nylon 6,6), 1,4-tetramethylenediamine/adipic acid (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-nonamethylenediamine/terephthalic acid/ε-caprolactam, 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid, and m-xylylenediamine/adipic acid can be heard Among these, 1,4-tetramethylenediamine/adipic acid (nylon 4,6), 1,6-hexamethylenediamine/terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, Poly obtained from 1,9-nonamethylenediamine/terephthalic acid, 1,9-nonamethylenediamine/terephthalic acid/ε-caprolactam, or 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid Amide resins are more preferred.

The content of the thermoplastic resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, still more preferably in the range of 5 to 45 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. am. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within this range, the effect of further improving heat resistance, chemical resistance and mechanical properties is obtained.

As the elastomer blended in the polyarylene sulfide resin composition, a thermoplastic elastomer is often used. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In addition, in this specification, thermoplastic elastomer is classified as an elastomer other than the said thermoplastic resin.

The elastomer (particularly the thermoplastic elastomer) preferably has a functional group capable of reacting with at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxy group, and a salt of a carboxyl group. This makes it possible to obtain a resin composition that is particularly excellent in terms of adhesiveness, impact resistance, and the like, and can suppress the amount of gas generated by heating. As such a functional group, an epoxy group, an amino group, a hydroxyl group, a carboxy group, a mercapto group, an isocyanate group, an oxazoline group, and formula: R(CO)O(CO)- or R(CO)O- (wherein R is carbon represents an alkyl group having 1 to 8 atoms). A thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the above functional group. Examples of the α-olefin include C2-C8 α-olefins such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having the 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, itaconic acid, and other carbon atoms of 4 to 100. 10 α, β-unsaturated dicarboxylic acids and derivatives thereof (mono- or diesters, and acid anhydrides thereof), glycidyl (meth)acrylate, and the like. Among these, the group consisting of an epoxy group, a carboxy group, and a group represented by the formula: R(CO)O(CO)- or R(CO)O- (wherein R represents an alkyl group having 1 to 8 carbon atoms) An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from are preferred from the standpoint of improving toughness and impact resistance.

Although the content of the elastomer is different depending on the type and use, it cannot be uniformly defined. For example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin. It is in the range of to 100 parts by mass, more preferably in the range of 5 to 45 parts by mass. When the content of the elastomer is within this range, further excellent effects are obtained in terms of securing the heat resistance and toughness of the molded product.

The crosslinkable resin blended in the polyarylene sulfide resin composition has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. As a crosslinkable resin, an epoxy resin, a phenol resin, and a urethane resin are mentioned, for example.

As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group or a hydroxyl group. Examples of suitable aromatic epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, and cresol no. Rockfish type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenolaralkyl type epoxy resin, naphthol novolak type epoxy resins, naphthol-phenol coaxial novolak-type epoxy resins, naphthol-cresol coaxial novolac-type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resins, and biphenyl novolak-type epoxy resins. can These aromatic epoxy resins can be used individually or in combination of 2 or more types. Among these aromatic epoxy resins, novolak-type epoxy resins are preferred, and cresol novolak-type epoxy resins are more preferred, from the viewpoint of excellent compatibility with other resin components.

The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. is the range When the content of the crosslinkable resin is within this range, the effect of improving the rigidity and heat resistance of the molded article is obtained particularly remarkably.

The polyarylene sulfide resin composition may contain a silane compound having a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, and a salt of a carboxy group. As a result, a resin composition capable of improving the compatibility of the polyarylene sulfide resin with other components and suppressing the amount of gas generated by heating can be obtained. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ- and silane coupling agents such as glycidoxypropylmethyldiethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

The content of the silane compound is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin, for example. When the content of the silane compound is within this range, the effect of improving the compatibility between the polyarylene sulfide resin and the other components described above is obtained.

The polyarylene sulfide resin composition according to the present embodiment may contain other additives such as a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant. It is preferable that content of an additive is the range of 1-10 mass parts with respect to 100 mass parts of polyarylene sulfide resins, for example.

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

The polyarylene sulfide resin composition according to the present embodiment, alone or in combination with materials such as the above other components, by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, has heat resistance, molding processability, It can be processed into molded products with excellent dimensional stability. The polyarylene sulfide resin composition according to the present embodiment enables easy production of high-quality molded articles because the amount of gas generated when heated is small.

The molded article obtained in this way is suitably used for a surface-mounted electronic component. A surface-mounted electronic component has, for example, a molded product of a polyarylene sulfide resin composition and a metal terminal as components, and is fixed on a printed wiring board or circuit board by a surface-mounting method. In order to fix this electronic component to the board by the surface mounting method, the metal terminal of the electronic component is placed on the board surface so that it is in contact with the conductive part on the board through the solder ball, and heated in the reflow furnace by the above heating method. Thereby, a method of soldering the electronic component to the board is exemplified. Specific examples of such surface-mounted electronic components include connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, housings of ICs and LEDs compatible with the surface-mounting system, and the like.

When the polyarylene sulfide resin composition according to the present embodiment is used for a surface-mounted electronic component, the amount of gas generated by heating can be reduced, so that corrosion of metal terminals and the like can be suppressed. In addition, according to the polyarylene sulfide resin composition according to the present embodiment, even when molded into a molded product having a snap-fit portion, for example, excellent mechanical strength is exhibited.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

1. Evaluation method

[bending properties]

・Compliant test method... ASTM D-790

・Test piece… 3.2mm (thickness) x 12.7mm (width) x 127mm (length)

·Test result… Mean value of n=10 tested

[Hot water resistance]

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

・Test piece… 3.2mm (thickness) x 12.7mm (width) x 127mm (length)

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

・Evaluation items… Retention rate of flexural strength to initial strength after 1000 hours and 3000 hours

·Test result… Mean value of the number of tests n = 5

[Metal Adhesion Strength]

A tensile test was performed under the conditions of 20 mm between chucks and 1 mm/min in tensile speed for a piece of polyarylene sulfide resin composition having the same dimensions injected and molded into a 4 × 10 × 49 mm metal piece (SUS304) set in a mold. was carried out to measure the metal adhesion strength.

[cavity balance]

Using a washer mold with 40 cavities, the PPS compound was injection molded under the minimum molding conditions in which the cavity (C1) located closest to the primary spool was completely filled. The molding conditions were a 75-ton molding machine, cylinder temperature of 320 ° C., mold temperature of 140 ° C., and no holding pressure.

After molding, the filling degree of the cavity (C10) furthest from the primary spool on the same runner as cavity (C1) was compared. The degree of filling (% by mass) was obtained from the mass ratio of the molded product of the cavity C10 to the molded product of the cavity C1. It can be said that the higher the filling degree of the cavity C10 is, the better the cavity balance is. Based on the degree of filling, the cavity balance of each composition was determined according to the following criteria.

AA: range of 100 to 90% by mass

A: range of 89 to 80% by mass

B: range of 79 to 70% by mass

C: range of 69 to 60% by mass

D: Range of 59% or less by mass

[Gas generation amount]

Using a gas chromatograph mass spectrometer, a sample of a predetermined amount of polyarylene sulfide resin or resin composition was heated at 325°C for 15 minutes, and the amount of gas generated at that time was quantified as mass%.

[Reflow Heatability]

Pellets of the resin composition were molded using an injection molding machine to create a box-shaped connector having a shape of 70 mm in length x 10 mm in width x 8 mm in height and 0.8 mm in thickness. Next, this box-type connector was placed on the printed circuit board and heated under the following reflow conditions. After heating, the box-shaped connector was visually observed, and external appearance was evaluated based on the following two-step criteria.

○: No change in appearance

×: blistering or melting was observed

(reflow condition)

Reflow heating was performed with an infrared reflow device (“TPF-2” manufactured by Asahi Engineering Co., Ltd.). As the heating conditions at this time, after preliminary heating at 180°C for 100 seconds, heating was maintained until the surface of the substrate reached 280°C. That is, the temperature profile (temperature curve) is set in the reflow device so that it is 100 seconds in the region of 200 ° C. or higher, 90 seconds in the region of 220 ° C. or higher, 80 seconds in the region of 240 ° C. or higher, and 60 seconds in the region of 260 ° C. or higher, Heating and holding were performed.

2. Synthesis of polyphenylene sulfide resin (PPS resin)

(Synthesis Example 1: Synthesis of PPS-1)

p-diiodobenzene (Tokyo Chemical Co., Ltd., p-diiodobenzene purity 98.0% or more) 300.0g, solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) 27.00g, 4 2.0 g of 4'-dithiobisbenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobisbenzoic acid, Technical Grade) was heated at 180°C, and they were dissolved and mixed under nitrogen. Next, the temperature was raised to 220°C and the pressure was reduced to an absolute pressure of 26.6 kPa. The obtained molten mixture was melt-polymerized for 8 hours at 320°C by changing the temperature and pressure stepwise so as to have an absolute pressure of 133 Pa. After completion of the reaction, 200 g of NMP was added, heated and stirred at 220°C, and the obtained lysate was filtered. 320 g of NMP was added to the lysate after filtration, and cake washing filtration was performed. 1 liter of ion-exchanged water was added to the obtained NMP-containing cake, and the mixture was stirred in an autoclave at 200°C for 10 minutes. Next, the cake was filtered, and 1 L of 70°C ion-exchanged water was added to the cake after the filtration to perform cake washing. 1 L of ion-exchanged water was added to the obtained water-containing cake, and the mixture was stirred for 10 minutes. Next, the cake was filtered, and 1 liter of 70°C ion-exchanged water was added to the cake after the filtration to perform cake cleaning. After repeating this operation once again, the cake was dried at 120°C for 4 hours to obtain 91 g of PPS resin (PPS-1).

(Synthesis Example 2: Synthesis of PPS-2)

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

(Synthesis Example 3: Synthesis of PPS-3)

91 g of PPS resin (PPS-3) was obtained in the same manner as in Synthesis Example 1 except that "diphenyl disulfide (Sumitomo Seika Co., Ltd., DPDS)" was used instead of "4,4'-dithiobisbenzoic acid."

(Synthesis Example 4: Synthesis of PPS-4)

600 g of N-methylpyrrolidone and 336.3 g (2.0 mol) of sodium sulfide pentahydrate were put into a 2-liter autoclave, and the water-NMP mixture was distilled off by raising the temperature to 200°C under a nitrogen atmosphere. Next, to this system, a solution of 292.53 g (1.99 mol) of p-dichlorobenzene and 1.62 g (0.01 mol) of 2,5-dichloroaniline dissolved in 230 g of NMP was added, followed by 5 hours at 220°C and further at 240°C. It was made to react in nitrogen atmosphere for 2 hours. After cooling from the reaction vessel, the contents were taken out, a part was sampled, and unreacted 2,5-dichloroaniline was quantified with a gas chromatograph. Further, the remaining slurry was washed several times with hot water, and the polymer cake was separated by filtration. This cake was dried under reduced pressure at 80°C to obtain powdery amino group-containing polyphenylene sulfide (PPS-4).

Table 1 shows the properties of PPS-1 to PPS-4 obtained in Synthesis Examples 1 to 4.

[Table 1]

[Raw material]

In order to prepare the PPS resin composition, the following materials were prepared.

(thermoplastic resin)

PA6T: Aromatic polyamide 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: Polyamide obtained by reacting nonanediamine with terephthalic acid (Kurare Co., Ltd., "Genesta N1000A")

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

(mineral filler)

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

[Production and evaluation of compound]

After uniformly mixing each raw material with a blending composition shown in Table 1 with a tumbler, it was melt-kneaded at 300 ° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Kikai) to obtain a pellet-shaped compound. The obtained compound was injection molded under the conditions of a cylinder temperature of 300°C and a mold temperature of 140°C, and test pieces to be used for tests of bending properties, metal adhesion strength, cavity balance, and hot water resistance were prepared and various evaluations were performed. In addition, the amount of gas generation was measured for the PPS resin alone and the compound. Table 2 shows the evaluation results.

[Table 2]

As is clear from the results shown in Table 2, PPS-1, PPS-2, and PPS-3 are mechanical properties (bending strength, bending elongation at break), metal adhesion strength, cavity balance, hot water resistance, gas generation amount, Better than PPS-4.

Claims (15)

A polyarylene sulfide resin;
At least one other component selected from the group consisting of thermoplastic resins other than the polyarylene sulfide resin, elastomers, and crosslinkable resins having two or more crosslinkable functional groups;
As a polyarylene sulfide resin composition for surface-mounted electronic components containing,
The polyarylene sulfide resin reacts a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the simple sulfur, and the polymerization inhibitor. It can be obtained by a method including
The polyarylene sulfide resin has at least one group selected from the group consisting of carboxy groups and salts of carboxy groups derived from the polymerization inhibitor,
The polyarylene sulfide resin has an Mw / Mtop of 0.80 to 1.70,
Wherein Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. delete According to claim 1,
The polyarylene sulfide resin,
In the main chain, the following general formula (20)

A polyarylene sulfide resin for surface-mounted electronic components, which is a mixture containing a polyarylene sulfide resin having a disulfide bond represented by , and an iodine atom in a ratio ranging from 0.01 to 10,000 ppm relative to the polyarylene sulfide resin. composition. delete According to claim 3,
In the main chain, the following general formula (20)

A polyarylene sulfide resin having a disulfide bond represented by
The following general formula (a) at the terminal

A monovalent group represented by the following general formula (b)

A monovalent group represented by, or the following general formula (c)

(However, X in general formulas (a) to (c) is a hydrogen atom or an alkali metal atom. In general formula (b), R ¹⁰ represents an alkylene group having 1 to 6 carbon atoms. General formula (c) ), R ¹¹ represents an alkylene group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms)] polyarylene sulfide resin for surface-mounted electronic components having a monovalent group represented by composition. According to claim 1,
The polyarylene sulfide resin composition for surface-mounted electronic parts in which the said polyarylene sulfide resin has a non-Newtonian index of 0.95-1.75 in 300 degreeC. According to claim 1,
A polyarylene sulfide resin composition for surface-mounted electronic parts further containing a fibrous filler. delete delete A polyarylene sulfide resin;
Melt-kneading at least one other component selected from the group consisting of thermoplastic resins other than the polyarylene sulfide resin, elastomers, and crosslinkable resins having two or more crosslinkable functional groups,
The polyarylene sulfide resin reacts a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodoaromatic compound, the elemental sulfur, and the polymerization inhibitor It is obtained by a method, and the polyarylene sulfide resin has at least one group selected from the group consisting of a carboxy group derived from the polymerization inhibitor and a salt of a carboxy group, and
The polyarylene sulfide resin has an Mw / Mtop of 0.80 to 1.70,
Wherein Mw and Mtop are weight average molecular weight and peak molecular weight measured by gel permeation chromatography, respectively. delete According to claim 10,
The manufacturing method of the polyarylene sulfide resin composition for surface-mounted electronic components in which the said polyarylene sulfide resin has a non-Newtonian index of 0.95-1.75 in 300 degreeC. According to claim 10,
A method for producing a polyarylene sulfide resin composition for surface-mounted electronic components further comprising a fibrous filler as a component melt-kneaded with the polyarylene sulfide resin. delete According to claim 10,
The polymerization inhibitor, the following general formula (3), (4) or (5)

[In formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and R ¹ Or at least any one of ^R2 is a monovalent group represented by general formula (a), (b) or (c). In general formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent group represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ represents a monovalent group represented by general formula (a), (b) or (c).

(However, X in general formulas (a) to (c) is a hydrogen atom or an alkali metal atom. In general formula (b), R ¹⁰ represents an alkylene group having 1 to 6 carbon atoms. General formula (c) ), wherein R ¹¹ represents an alkylene group having 1 to 3 carbon atoms and R ¹² represents an alkyl group having 1 to 5 carbon atoms)] polyarylene sulfide resin for surface-mounted electronic components containing a compound represented by A method for preparing the composition.