KR20160065835A - Polyarylene sulfide resin composition and molded product thereof, and surface-mount electronic component - Google Patents

Abstract

A polyarylene sulfide resin composition, a molded article using the resin composition, and an electronic part comprising the molded article, which can suppress an amount of gas generation by heating and have excellent properties in a resin composition or a molded article thereof, are provided. Specifically, it is preferable to use at least one other component selected from the group consisting of a polyarylenesulfide resin and an inorganic filler, a thermoplastic resin other than the polyarylenesulfide resin, an elastomer, and a crosslinkable resin having at least two crosslinkable functional groups Wherein the polyarylenesulfide resin comprises a diiodo aromatic compound, a grouped sulfur, and a polymerization inhibitor in combination with a diiodo aromatic compound, a grouped sulfur, and a polymerization initiator In a molten mixture containing an inhibitor, a polyarylenesulfide resin composition for surface-mounted electronic parts, a molded article using the resin composition, and an electronic part comprising the molded article.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyarylene sulfide resin composition, a molded article thereof, and a surface mounted electronic component,

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

2. Description of the Related Art In recent years, in the field of the electric and electronic industry, with the miniaturization of products and the improvement of productivity, the mounting method of a resin-based electronic component on a printed board has been referred to as a surface mounting method Called surface mounting method. Conventionally, a tin-lead eutectic solder (melting point: 184 DEG C) was generally used for mounting electronic components on a substrate by the SMT method. In recent years, however, in view of environmental pollution, Lead-free solder is used in which some kinds of metal are added as a base.

This lead-free solder has a melting point higher than that of tin-lead process solder. For example, in the case of tin-silver process solder, the melting point reaches 220 캜, so the temperature of the heating furnace (reflow) I had to raise it. Therefore, there is a problem in that, when soldering a resin-based electronic component such as a connector, the electronic component is melted or deformed in a heating furnace (reflow furnace). Therefore, resin materials used for surface-mounted electronic parts are strongly required to have high heat resistance.

On the other hand, a polyarylenesulfide resin represented by polyphenylene sulfide resin (hereinafter may be abbreviated as "PPS resin" hereinafter) (hereinafter sometimes abbreviated as "PAS resin") as a high heat resistant resin material And a molded product of the resin composition containing the polyarylenesulfide resin and a surface-mounted electronic component provided with a metal terminal suppress the melting or deformation of the electronic component even in a heating furnace (reflow furnace) (See, for example, Patent Document 1).

International Publication No. 2009/096401

However, in a conventional composition containing a polyarylenesulfide resin, the amount of gas generated by heating during molding and the like is relatively large, which may cause corrosion of metal terminals of electronic parts. Further, in the conventional polyarylenesulfide resin compositions or molded articles thereof, the properties such as mechanical strength, metal adhesion, and cavity balance have still to be improved.

Therefore, a problem to be solved by the present invention is to prevent the surface-mounted electronic component from being melted or deformed in the heating furnace (reflow furnace) while suppressing the amount of gas generated by heating, A molded product using the resin composition, and a surface-mounted electronic component comprising the molded product, which have excellent mechanical strength, metal adhesion, and cavity balance characteristics.

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

That is, the present invention relates to a resin composition comprising a polyarylenesulfide resin and at least one kind selected from the group consisting of an inorganic filler, a thermoplastic resin other than the polyarylenesulfide resin, an elastomer, and a crosslinkable resin having at least two crosslinkable functional groups A polyarylenesulfide resin composition for surface mount electronic components, which contains other components, wherein the polyarylenesulfide resin comprises a diiodo aromatic compound, a single sulfur, a polymerization inhibitor , A diiodo aromatic compound, a group sulfur, and a polymerization inhibitor in a molten mixture. The present invention also relates to a polyarylenesulfide resin composition for surface mounted electronic components.

According to the present invention, it is possible to prevent the surface mounted electronic component from melting or deforming in the heating furnace (reflow furnace), and also to suppress the amount of gas generated by heating, and further, in the resin composition or the molded product thereof, 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 comprising the molded article.

The cavity balance is related to the uniformity of filling degree of each cavity when a plurality of molded articles are simultaneously molded by injection molding using a mold having a plurality of cavities. If the cavity of the molding material is not sufficiently balanced, there is a tendency that molding defects that some of the cavities are not sufficiently filled tend to occur.

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

The polyarylenesulfide resin used in this embodiment is produced by reacting a diiodo aromatic compound, a group sulfur and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, a group sulfur and a polymerization inhibitor And the like. According to this method, a polyarylenesulfide resin can be obtained as a relatively high molecular weight polymer as compared with the conventional method including the Phillips method.

A diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to an aromatic ring. Examples of the diiodo aromatic compound include diiodobenzene, diiodotoluene, diiodo xylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether, and diiododi Phenyl sulfone, and the like, but are not limited thereto. The substitution position of two iodine atoms is not particularly limited, but preferably two substitution positions are located as far as possible in the molecule. Preferred substitution positions are para position, and 4,4'-position.

The aromatic ring of the diiodo aromatic compound may be at least one selected from the group consisting of a phenyl group, a halogen atom other than an iodine atom, a hydroxy group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carboxylate, an arylsulfone, And may be substituted by a substituent of the species. However, in view of the crystallinity and heat resistance of the polyarylenesulfide 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 mass% And preferably from 0.001 to 1% by mass.

Grouped sulfur means a substance (S ₈ , S ₆ , S ₄ , S _2, etc.) composed only of sulfur atoms, and its form is not limited. Concretely, a commercially available sulfur group may be used as a defense medicinal product, or a mixture containing S ₈ and S ₆ or the like, which can be obtained in general terms, may be used. The purity of the grouped sulfur is also not particularly limited. If grouped sulfur is solid at room temperature (23 ° C), it may be granular or powdery. The particle size of the grouped 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, and more preferably in the range of 0.01 to 3 mm.

The polymerization inhibitor can be used without particular limitation as long as it is a compound which inhibits or stops the polymerization reaction in the polymerization reaction of the polyarylenesulfide resin. The polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a carboxyl group at the end of the main chain of the polyarylenesulfide resin. That is, as the polymerization inhibitor, a compound having at least one kind of group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and a salt of a carboxyl group is preferable. In addition, the polymerization inhibitor may have the functional group, or the functional group may be produced by stopping the polymerization or the like.

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

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

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

The group represented by the formula (1-1) or (2-1) is a group in which a disulfide bond derived from a raw material (a group of sulfur) in a main chain of a polyarylenesulfide resin undergoes radical cleavage Radical is bonded to a compound represented by the general formula (1) or a compound represented by the general formula (2), it is considered to be introduced into the polyarylenesulfide resin. The presence of the constitutional unit of these specific structures is characteristic of the polyarylenesulfide resin obtained by melt polymerization using the compound represented by the general formula (1) or (2).

Examples of the compound represented by the general formula (1) include 2-iodophenol and 2-aminoaniline. The compound represented by the general formula (2) includes 2-iodobenzophenone.

As the polymerization inhibitor having a carboxyl group, for example, at least one compound selected from the compounds represented by the following general formula (3), (4) or (5) may be used.

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

X in the formulas (a) to (c) is a hydrogen atom or an alkali metal atom, but a hydrogen atom is preferable in that the reactivity becomes good. Examples of the alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, but sodium is preferable. In the general formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In the general formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹² represents an alkyl group of 1 to 5 carbon atoms.

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

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

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

As the polymerization inhibitor, a compound having no functional group such as a carboxyl group or the like may be used. Such compounds include, for example, diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl- At least one kind of compound selected from morpholinone, zolylsulfenamide, 2- (morpholinothio) benzothiazole and N, N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.

The polyarylenesulfide 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, a sulfur group, 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 0.8 to 1.2 moles, per 1 mole of the group sulfur. The ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mole, more preferably 0.0005 to 0.05 mole, per mole of solid sulfur.

The time when the polymerization inhibitor is added is not particularly limited, but it is preferable to heat the mixture containing the diiodo aromatic compound, the group sulfur and the catalyst optionally added, so that the temperature of the mixture is preferably 200 ° C to 320 ° C And more preferably 250 to 320 캜, the polymerization inhibitor may be added.

By adding a nitro compound as a catalyst to the molten mixture, the polymerization rate can be controlled. As the nitro compound, various nitrobenzene derivatives can be generally 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-4-nitroamine. The amount of the catalyst is usually in an amount to be added as a catalyst, and is preferably in a range of 0.01 to 20 parts by mass with respect to 100 parts by mass of sulfur.

The conditions of the melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably 175 占 폚 or higher, the melting point of the polyarylenesulfide resin to be produced + 100 占 폚 or lower, and more preferably 180 to 350 占 폚. The molten polymerization is carried out at an absolute pressure preferably in the range of 1 [cPa] to 100 [mm], more preferably in the range of 13 [cPa] to 60 [mm]. The conditions of the melt polymerization need not be constant. For example, in the initial stage of the polymerization, the temperature is preferably in the range of 175 to 270 DEG C, more preferably 180 to 250 DEG C, and the absolute pressure is set in the range of 6.7 to 100 [ And the polymerization is carried out at a temperature of preferably 270 DEG C or higher and a melting point of the produced polyarylenesulfide resin + 100 DEG C or lower, more preferably 300 to 350 DEG C Deg.] C and the absolute pressure is in the range of 1 [cPa] to 6 [deg.]. In the present specification, the melting point of the resin means a value measured in accordance with JIS K 7121 using a differential scanning calorimeter (Pyris Diamond DSC apparatus, Perkin Elmer).

The melt polymerization is preferably carried out in a non-oxidizing atmosphere from the viewpoint of obtaining a high polymerization degree while preventing the oxidation crosslinking reaction. In the non-oxidizing atmosphere, the oxygen concentration in the gaseous phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, and more preferably the gas phase is substantially free of oxygen . The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium and 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 kneader 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 per 100 parts by mass of the total amount of the diiodo aromatic compound, the group sulfur, the polymerization inhibitor and, if necessary, the catalyst More preferably not more than 5 parts by mass, and still more preferably not more than 1 part by mass. The amount of the solvent may be in the range of 0 mass part or more, 0.01 mass part or more, or 0.1 mass part or more.

After the molten mixture (reaction product) after the melt polymerization is cooled to obtain a solid mixture, the mixture may be heated under reduced pressure or atmospheric pressure in a non-oxidizing atmosphere to further proceed the polymerization reaction. As a result, not only the molecular weight can be further increased but also the iodine molecules produced are sublimated and removed, so that the iodine atom concentration in the polyarylenesulfide resin can be suppressed to a low level. Preferably in the range of 100 to 260 占 폚, more preferably in the range of 130 to 250 占 폚, and more preferably in the range of 150 to 230 占 폚. Heating after cooling to a solid state can be carried out under the same temperature and pressure conditions as in the melt polymerization.

The reaction product containing the polyarylenesulfide resin obtained by the melt polymerization process may be directly added to the melt kneader as it is, but the resin composition may be prepared by dissolving the reaction product in a solvent To prepare a melt and to take out the reaction product from the reactor in the state of the dissolved product is preferable because not only the productivity but also the reactivity becomes better. The addition of the solvent in which the reaction product dissolves is preferably carried out after the melt polymerization, but may be carried out at a later stage of the reaction of the melt polymerization, and the molten mixture (reaction product) may be cooled as described above to obtain a solid mixture The mixture may be heated to proceed the polymerization reaction further under pressure, under reduced pressure, or under atmospheric pressure in a non-oxidizing atmosphere. The step of preparing the melt may be performed in a non-oxidizing atmosphere. The temperature for the heating and dissolution may be in the range of the melting point of the solvent in which the reaction product is dissolved, preferably in the range of 200 to 350 캜, more preferably in the range of 210 to 250 캜, .

The mixing ratio of the solvent to be dissolved in the reaction product used for preparing 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 with respect to 100 parts by mass of the reaction product containing the polyarylene sulfide resin Is in the range of 200 to 400 parts by mass.

As the solvent in which the reaction product is dissolved, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as the Philips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter, abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, (HMPA), tetramethyl urea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMF). The aliphatic cyclic amide compounds may be used alone or in combination of two or more. (DMA); etherified polyethylene glycol compounds such as polyethylene glycol dialkyl ether (having a degree of polymerization of not more than 2000 and having an alkyl group of 1 to 20 carbon atoms); and etherified polyethylene glycol compounds such as tetramethylene sulfoxide and dimethyl sulfoxide (DMSO), and the like. Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4'-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4- Benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, dibenzothiophene, dibenzothiophene, dibenzothiophene, dibenzothiophene, Benzene naphthalene, 1-bromophenol, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidone, Dienone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylbiphenyl, 1,1- 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4, 6-diphenylanthraquinone, 4'- 4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenyl phthalate , Diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromodiphenyl ether, pyrene, 9,9'-non-fluorene, 4,4'-isopropylidene At least one solvent selected from the group consisting of diphenol, epsilon -caprolactam, N-cyclohexyl-2-pyrrolidone, diphenylisophthalate, diphenylterephthalate and 1-chloronaphthalene.

The melt taken out from the reactor is preferably subjected to a post-treatment and then melt-kneaded with the other components to prepare a resin composition because the reactivity becomes better. The method for the post-treatment of the melt is not particularly limited, and for example, the following methods can be mentioned.

(1) The solvent is removed as it is, or an acid or a base is added thereto, and the solvent is distilled off under reduced pressure or at atmospheric pressure. Subsequently, the solid substance after distillation of the solvent is dissolved in water and a solvent (or a low molecular polymer Washing with a solvent selected from acetone, methyl ethyl ketone, alcohols and the like, followed by further neutralization, washing with water, filtration and drying.

(2) A method for producing a water-soluble organic solvent which is soluble in a solvent of the soluble solute, such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon and aliphatic hydrocarbon, A solvent which is a poor solvent for the resin) as a sedimentation agent to sediment a solid product including a polyarylenesulfide resin and an inorganic salt, and filtering the solid product by filtration, washing and drying.

(3) The solvent used for the melt (or an organic solvent having the solubility equivalent to that of the low molecular polymer) is added to the melt, and the mixture is stirred to remove the low molecular weight polymer. Then, water, acetone, Alcohol, and the like, followed by neutralization, washing with water, filtration, and drying.

In the post-treatment method as exemplified in (1) to (3) above, drying of the polyarylenesulfide resin may be performed in a vacuum, or in an air or an inert gas atmosphere such as nitrogen. The polyarylenesulfide resin may be subjected to an oxidative crosslinking treatment in an oxidizing atmosphere having an oxygen concentration of 5 to 30% by volume or under a reduced pressure condition.

The reaction that the polyarylenesulfide resin produces by the melt polymerization is exemplified below.

Reaction formulas (1) to (5) are examples in which diphenyl disulfide having a substituent R containing a group represented by the general formula (a), (b) or (c) This is an example of the reaction that the polyphenylsulfur feed generates. Reaction formula (1) is a reaction in which the -S-S- bond in the polymerization inhibitor radically cleaves at a melting temperature. In the reaction formula (2), the sulfur radicals generated in the reaction formula (1) attack the adjacent carbon atoms of the terminal iodine atom of the growing main chain to desorb the iodine atom, and the polymerization is stopped and the substituent R is introduced . Reaction formula (3) is a radical cleavage reaction of a disulfide bond derived from a raw material (a single sulfur) in a main chain of a polyarylenesulfide resin at a melting temperature. Reaction formula (4) is a reaction in which polymerization is stopped by introducing a sulfur radical generated in reaction formula (3) and a sulfur radical generated in reaction formula (1), and substituent R is introduced to the end of the main chain. The iodine atom which is eliminated is in a free state (iodine radical), or iodine radicals are recombined with each other as in the reaction formula (5), and iodine molecules are produced.

The reaction product containing the polyarylene sulfide resin obtained by the melt polymerization contains iodine atoms derived from the raw material. For this reason, the polyarylenesulfide resin is usually used in the form of a mixture containing an iodine atom for the preparation of a resin composition for dispersion. The concentration of the iodine atom in the mixture is, for example, in the range of 0.01 to 10000 ppm, preferably in the range of 10 to 5000 ppm, based on the polyarylenesulfide resin. It is also possible to suppress the iodine atom concentration to a low level by using the sublimation property of the iodine molecule. In this case, the iodine atom concentration can be suppressed to 900 ppm or less, preferably 100 ppm or less and 10 ppm or less. It is also possible to remove the iodine atoms below the detection limit, but this is not practical considering the productivity. The detection limit is, for example, about 0.01 ppm. The polyarylenesulfide resin of the present embodiment obtained by the melt polymerization or the reaction product containing the iodine atom of the present invention can be obtained by solution polymerization in an organic polar solvent such as a Phillips method, Can be clearly distinguished from the polyarylenesulfides obtained by the method.

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

The polyphenylsulfurpide resin as the polyarylenesulfide resin according to one embodiment includes, for example, a compound represented by the following general formula (10):

(Arylene sulfide unit) represented by the following general formula (1). The repeating unit represented by the formula (10) is a repeating unit represented by the following formula (10a):

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

Is more preferable. Among them, the repeating unit bonded at the para position represented by the formula (10a) is preferable in view of heat resistance and crystallinity of the resin.

The polyphenylsulfurpide resin according to one embodiment is a polyphenylsulfide resin represented by the following general 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 amino group, a phenyl group, a methoxy group or an ethoxy group) And a repeating unit having a substituent as a side chain. However, it is preferable that the polyphenylsulfide resin does not substantially contain the repeating unit of the formula (11) from the viewpoints of the deterioration of the crystallinity and the heat resistance. More specifically, the proportion of the repeating unit represented by the formula (11) is preferably not more than 2% by mass relative to the total of the repeating unit represented by the formula (10) and the repeating unit represented by the formula (11) , And more preferably 0.2 mass% or less.

The polyarylenesulfide resin of the present embodiment is mainly composed of the above-mentioned arylene sulfide feed units, but usually has a structure represented by the following formula (20):

Also includes the constitutional unit according to the disulfide bond represented by the formula (I) in the main chain. The proportion of the constituent unit represented by the formula (20) is preferably 2.9% by mass or less based on the total of the arylene sulfide unit and the constituent unit represented by the formula (20) in terms of heat resistance and mechanical strength , And more preferably 1.2 mass% or less. The polyarylenesulfide resin preferably contains the structural unit represented by the formula (20) in that the adhesion between the polyarylenesulfide resin composition and the metal improves.

The Mw / Mtop of the polyarylenesulfide 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. When the Mw / Mtop is within this range, the workability of the polyarylenesulfide resin can be improved, and a good cavity balance can be obtained. 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 which the detection intensity of the chromatogram obtained by the same measurement becomes maximum. Mw / Mtop represents the distribution of the molecular weight of the object to be measured. Typically, when this value is close to 1, the distribution of the molecular weight is narrow, and as the value is larger, the distribution of the molecular weight is broad. The measurement conditions of the gel permeation chromatography are the same measurement conditions as in the examples of this 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 polyarylenesulfide resin according to this embodiment is not particularly limited as long as it does not impair the effect of the present invention. The lower limit of the polyarylenesulfide resin is preferably 28,000 or more in view of excellent mechanical strength, Is more preferable. On the other hand, the upper limit is preferably within a range of 100,000 or less, more preferably within a range of 60,000 or less, and further preferably within a range of 55,000 or less, from the viewpoint of providing a better cavity balance. In addition, from the viewpoint of excellent mechanical strength and good cavity balance, a polyarylenesulfide resin in a range of 28,000 to 60,000, more preferably a polyarylenesulfide resin in a range of 30,000 to 55,000 A polyarylenesulfide resin having a weight average molecular weight in the range of from 60,000 to 100,000 may be used.

The nonylenic index of the polyarylenesulfide resin is preferably in the range of 0.95 to 1.75, and more preferably in the range of 1.0 to 1.70. By setting the non-neutron index to this range, the workability of the polyarylenesulfide resin can be improved, and a good cavity balance can be provided. In the present specification, the non-neutron index refers to an index that satisfies the following relational expression between shear rate and shear stress under the condition of a temperature of 300 캜. The Nietzschean index can be an index relating to the molecular weight of the object to be measured or a molecular structure such as linear chain, branching and crosslinking. Usually, when the value is close to 1, the molecular structure of the resin is linear, As this value increases, it indicates that many branched or crosslinked structures are included.

D = α × S ⁿ

(Wherein D represents a shear rate, S represents shear stress,? Represents a constant, and n represents a non-neutron index)

The polyarylenesulfide resin having a Mw / Mtop and a Nietzschean index of the above-mentioned specific range can be obtained by, for example, mixing a diiodo aromatic compound, a group sulfur and a polymerization inhibitor with a diiodo aromatic compound, (Solution polymerization) in a molten mixture containing a polymerization initiator and a polymerization inhibitor, it is possible to obtain such a polyarylenesulfide resin by increasing the molecular weight to some extent.

The melting point of the polyarylenesulfide resin according to this embodiment is preferably in the range of 250 to 300 캜, more preferably in the range of 265 to 300 캜. The melt viscosity (V6) of the polyarylenesulfide resin at 300 캜 is preferably in the range of 1 to 2000 [Pa · s], more preferably in the range of 5 to 1700 [Pa · s]. The melt viscosity V6 was measured using a flow tester for 6 minutes at a temperature of 300 占 폚 under a load of 1.96 MPa using an orifice having an orifice length and an orifice diameter ratio (orifice length / orifice diameter) of 10/1 The term " melt viscosity "

The polyarylene sulfide resin composition according to the present embodiment may contain one or two or more inorganic fillers. By incorporating an inorganic filler, a composition having high rigidity and high heat stability (high heat stability) can be obtained. Examples of the inorganic filler include powdery fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate fillers such as talc and mica, fillers such as glass beads, silica beads and glass balloons, Fibrous fillers such as carbon fibers and wollastonite fibers, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, 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, and more preferably in the range of 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylenesulfide resin to be. When the content of the inorganic filler is in this range, a more excellent effect can be obtained in terms of maintaining the mechanical strength of the molded article.

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

Examples of the thermoplastic resin to be blended in the polyarylene sulfide resin composition include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyetheretherketone, Polyether ketone, polyethylene, polypropylene, polytetrafluoroethylene, polytetrafluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester and the like).

The polyamide is a polymer having an amide bond (-NHCO-). Examples of the polyamide resin include (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) polymers obtained by ring- have. The polyamides may be used alone or in combination of two or more.

Examples of the diamine for obtaining the polyamide include aliphatic diamines, aromatic diamines, and alicyclic diamines. As the aliphatic diamine, a diamine having 3 to 18 carbon atoms having a straight chain or a side chain is preferable. Examples of suitable aliphatic diamines are 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, Octadecylenediamine, 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, , 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 may be used alone or in combination of two or more.

The aromatic diamine is preferably a diamine having 6 to 27 carbon atoms and having a phenylene group. Examples of customary aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 3,4-diaminodiphenyl ether, Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'- Di (p-aminophenoxy) diphenylsulfone, benzidine, 3,3'-diaminobenzophenone, 4,4'-di 4,4'-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 1,5-diaminonaphthalene, 1,8- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3- Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene and 4,4'- , 5'-dimethyldiphenylmethane, 4,4'-diamine 3,3 can be given a ', 5,5'-tetramethyl-diphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethyl benzidine.

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

The alicyclic diamine is preferably a diamine having 4 to 15 carbon atoms and having a cyclohexylene group. Examples of suitable alicyclic diamines include 4,4'-diamino-dicyclohexylene methane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl - dicyclohexylene methane, 1,4-diaminocyclohexane, and piperazine. These may be used alone or in combination of two or more.

Examples of dicarboxylic acids for obtaining polyamides 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, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecanedioic, Diacid, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These may be used alone or in combination of two or more.

As the aromatic dicarboxylic acid, a dicarboxylic acid having a phenylene group and having 8 to 15 carbon atoms is preferable. Examples of customary aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methylterephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid , Diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and 1,4- . These may be used alone or in combination of two or more. In addition, multivalent carboxylic acids such as trimellitic acid, trimethic acid, and pyromellitic acid may be used within the scope of melt molding.

As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferable. Examples of customary aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 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 lactam for obtaining the polyamide include ε-caprolactam, ω-laurolactam, ζ-enol lactam, and η-capryllactam. These may be used alone or in combination of two or more.

Preferred examples of the combination of raw materials of polyamide include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine / adipic acid (nylon 6,6), 1,4-tetramethylenediamine / adipic acid , 6), 1,6-hexamethylenediamine / terephthalic acid, 1,6-hexamethylenediamine / terephthalic acid / epsilon -caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / Terephthalic acid, 1,9-nonamethylene diamine / terephthalic acid / epsilon -caprolactam, 1,9-nonamethylene diamine / 1,6-hexamethylene diamine / terephthalic acid / adipic acid, and m-xylenediamine / adipic acid . Among them, 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthalic acid / epsilon -caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylene diamine / terephthalic acid, 1,9-nonamethylene diamine / terephthalic acid / epsilon -caprolactam or 1,9-nonamethylene diamine / 1,6-hexamethylene diamine / 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, and more preferably in the range of 5 to 45 parts by mass with respect to 100 parts by mass of the polyarylenesulfide resin to be. When the content of the thermoplastic resin other than the polyarylenesulfide resin is within this range, an effect of further improving the 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 a polyolefin elastomer, a fluorine elastomer and a silicone elastomer. In this specification, the thermoplastic elastomer is classified as an elastomer other than the thermoplastic resin.

The elastomer (particularly, the thermoplastic elastomer) preferably has a functional group capable of reacting with at least one kind of group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and a salt of a carboxyl group. This makes it possible to obtain a resin composition which is particularly excellent in adhesiveness, impact resistance, and the like and which can suppress the amount of gas generated by heating. Examples of such a functional group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyanate group, an oxazoline group and a group represented by the formula: R (CO) O (CO) - or R (CO) Represents an alkyl group having 1 to 8 atoms). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an? -Olefin and a vinyl polymerizable compound having a functional group. Examples of the? -olefin include? -olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having a functional group include?,? - unsaturated carboxylic acids and alkyl esters thereof such as (meth) acrylic acid and (meth) acrylic acid esters, maleic acid, fumaric acid, itaconic acid, ? -Unsaturated dicarboxylic acids and derivatives thereof (mono or diesters, and acid anhydrides thereof), and glycidyl (meth) acrylate. Among them, a group consisting of an epoxy group, a carboxyl 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) And ethylene-butene copolymers having at least one functional group selected from the group consisting of ethylene-propylene copolymer and ethylene-butene copolymer are preferable from the viewpoint of improvement of toughness and impact resistance.

The content of the elastomer varies depending on the type and application thereof, and therefore can not be uniformly defined. For example, the content of the elastomer is preferably in the range of 1 to 300 parts by mass, more preferably 3 To 100 parts by mass, and more preferably 5 to 45 parts by mass. When the content of the elastomer is in this range, a further excellent effect can be obtained in terms of securing the heat resistance and toughness of the molded article.

The crosslinkable resin to be 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 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.

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 customary 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 novolak type epoxy resins, Phenol aralkyl type epoxy resins, naphthol novolak type epoxy resins, naphthol type epoxy resins, naphthol type epoxy resins, naphthol type epoxy resins, naphthol type epoxy resins, Cresol novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin denatured phenol resin type epoxy resin, and biphenyl novolac type epoxy resin are used in combination. . These aromatic epoxy resins may be used alone or in combination of two or more. Among these aromatic epoxy resins, novolak type epoxy resins are preferable, and cresol novolak type epoxy resins are more preferable because they are excellent in 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 3 to 100 parts by mass, and still more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the polyarylenesulfide resin Range. When the content of the crosslinkable resin falls within this range, the effect of improving the rigidity and heat resistance of the molded article can be remarkably obtained.

The polyarylenesulfide 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 hydroxyl group, an amino group, a carboxyl group and a salt of a carboxyl group. Thereby, it is possible to obtain a resin composition capable of improving the compatibility of the polyarylenesulfide resin with other components and suppressing the amount of gas generation by heating. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- And silane coupling agents such as glycidoxypropylmethyldiethoxysilane and? -Glycidoxypropylmethyldimethoxysilane.

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

The polyarylene sulfide resin composition according to the present embodiment may contain other additives such as a releasing agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant and a lubricant. The content of the additive is preferably in the range of, for example, 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylenesulfide resin.

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

The polyarylenesulfide resin composition according to the present embodiment can be obtained by heat treatment, molding processability, heat treatment, or the like by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, alone or in combination with the above- Dimensional stability and the like. The polyarylenesulfide resin composition according to the present embodiment has a small amount of gas to be generated when heated, thereby enabling easy manufacture of a high-quality molded article.

The thus obtained molded article is used for surface-mounted electronic parts. The surface-mounted electronic component is, for example, a molded product of a polyarylene sulfide resin composition and a metal terminal as constituent elements, and is fixed on a printed wiring printed circuit board or a circuit board by surface mounting. In order to fix the electronic component to the substrate by the surface mounting method, the metal terminal of the electronic component is placed on the substrate surface so as to be in contact with the conductive portion on the substrate via the solder ball and heated in the reflow furnace by the above- And then soldering the electronic component to the substrate. Specific examples of such a surface mount electronic component include a connector, a switch, a sensor, a resistor, a relay, a capacitor, a socket, a jack, a fuse holder, a coil bobbin, a housing of an IC or an LED for surface mounting.

When the polyarylenesulfide 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. Further, the polyarylenesulfide resin composition according to the present embodiment exhibits excellent mechanical strength even when molded into a molded article having, for example, a snap-fit portion.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

1. Evaluation Method

[Bending characteristics]

· Reference test method ... ASTM D-790

· Specimen ... 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (length)

·Test result… Mean value of test number n = 10

[Heat water resistance (heat resistant water resistance)]

The test piece was immersed in hot water at 95 캜, and the change in the bending strength with time was examined.

· Specimen ... 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (length)

· Test method of bending strength ... ASTM D-790

· Evaluation items ... 1000 hours and 3000 hours after the initial strength of the bending strength

·Test result… Mean value of test number n = 5

[Metal adhesion strength]

A polyarylenesulfide resin composition having the same dimensions was injected and molded into a metal piece (SUS304) having a size of 4 x 10 x 49 mm set on a mold, and a tensile test was conducted under the conditions of a chuck distance of 20 mm and a tensile speed of 1 mm / min And the metal adhesion strength was measured.

[Cavity balance]

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

The degree of filling of the cavity C10 farthest from the primary spool in the runner such as the cavity C1 after molding was compared. The degree of filling (mass%) was obtained from the mass ratio of the molded product of the cavity C10 to the molded product of the cavity C1. 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 based on the following criteria.

AA: a range of 100 to 90 mass%

A: a range of 89 to 80 mass%

B: a range of 79 to 70 mass%

C: a range of 69 to 60 mass%

D: a range of not more than 59% by mass

[Amount of gas generation]

Using a gas chromatograph mass spectrometer, a predetermined amount of the polyarylenesulfide resin or the resin composition was heated at 325 DEG C for 15 minutes, and the gas generation amount at that time was quantified as mass%.

[Flow-down heating property]

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

○: No change in appearance

X: Blister or melting observed

(Reflow conditions)

The reflow heating was performed with an infrared reflow apparatus (Asahi Engineering Co., Ltd. "TPF-2"). As the heating conditions at this time, preheating was carried out at 180 ° C for 100 seconds, respectively, and then heated and held until the surface of the substrate reached 280 ° C. That is, the temperature profile (temperature curve) is set in the reflow apparatus such that the temperature profile is set at 200 ° C or higher for 100 seconds, 220 ° C or higher for 90 seconds, 240 ° C or higher for 80 seconds, or 260 ° C or higher for 60 seconds, Followed by heating and holding.

2. Synthesis of polyphenylsulfide resin (PPS resin)

(Synthesis Example 1: Synthesis of PPS-1)

300.0 g of p-diiodobenzene (purity of 98.0% or more p-diiodobenzene manufactured by Tokyo Chemical Industry Co., Ltd.), 27.00 g of solid sulfur (manufactured by Kanto Kagaku Co., Ltd., sulfur (powder) , And 4'-dithiobenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobenzoic acid, Technical Grade) were heated to 180 ° C and dissolved and mixed under nitrogen. Next, the temperature was raised to 220 캜, and the pressure was reduced to 26.6 절대 absolute pressure. The obtained molten mixture was melted and polymerized at a temperature of 320 DEG C and an absolute pressure of 133Pa in a stepwise manner under pressure and pressure for 8 hours. After completion of the reaction, 200 g of NMP was added and the mixture was heated and stirred at 220 DEG C, and the resulting melt was filtered. After the filtration, 320 g of NMP was added to the melt, and the cake was filtered and cleaned. To the cake containing the obtained NMP, 1 liter of ion-exchanged water was added, and the mixture was stirred in an autoclave at 200 DEG C for 10 minutes. Next, the cake was filtered, and 1 liter of ion-exchanged water at 70 占 폚 was added to the cake after filtration to wash the cake. One liter of ion exchange water was added to the obtained functional cake, and the mixture was stirred for 10 minutes. Next, the cake was filtered, and 1 liter of ion-exchanged water at 70 占 폚 was added to the cake after filtration to wash the cake. After repeating this operation, the cake was dried at 120 ° C for 4 hours to obtain 91 g of a PPS resin (PPS-1).

(Synthesis Example 2: Synthesis of PPS-2)

91 g of PPS resin (PPS-2) 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 4,4'-dithiobenzoic acid .

(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 (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 sulfate 5 hydrate were charged into a 2-liter autoclave, and the water-NMP mixture was distilled off by raising the temperature to 200 ° C in a nitrogen atmosphere. Next, a solution of 292.53 g (1.99 mol) of p-dichlorobenzene and 1.62 g (0.01 mol) of 2,5-dichloroaniline in 230 g of NMP was added to this system, and the mixture was stirred at 220 ° C. for 5 hours, For 2 hours under a nitrogen atmosphere. After cooling from the reaction vessel, the contents were taken out, a portion of the sample was sampled, and unreacted 2,5-dichloroaniline was quantified by a gas chromatograph. 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 占 폚 to obtain an amino group-containing polyphenylsulfur feed (PPS-4).

Table 1 shows the properties of the 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: An aromatic polyamide obtained by reacting 65 mol% of terephthalic acid, 25 mol% of isophthalic acid and 10 mol% of adipic acid as an essential monomer component (melting point: 310 DEG C, Tg: 120 DEG C)

PA9T: Polyamide ("Genesta N1000A" manufactured by Kabushiki Kaisha Kureha Co., Ltd.) obtained by reacting nonanediamine with terephthalic acid,

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

(Inorganic filler)

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

[Production and evaluation of compound]

Each of the raw materials was uniformly mixed by a tumbler in the mixing composition shown in Table 1, and then melt-kneaded at 300 ° C using a twin-screw kneading extruder (TEM-35B, Toshiba Kiki) to obtain a pellet-shaped compound. The obtained compound was subjected to injection molding under the conditions of a cylinder temperature of 300 캜 and a mold temperature of 140 캜 to prepare test pieces for use in bending properties, metal adhesion strength, cavity balance and resistance to hot water resistance, and various evaluations were carried out. In addition, the gas generation amount was measured for the PPS resin alone and the compound. The evaluation results are shown in Table 2.

[Table 2]

As is apparent from the results shown in Table 2, PPS-1, PPS-2 and PPS-3 exhibited excellent mechanical properties in terms of mechanical properties (bending strength, bending elongation at break), metal adhesion strength, It was better than PPS-4.

Claims (6)

A polyarylenesulfide resin,
An inorganic filler, at least one other component selected from the group consisting of a thermoplastic resin other than the polyarylenesulfide resin, an elastomer, and a crosslinkable resin having at least two crosslinkable functional groups,
A polyarylene sulfide resin composition for surface mount electronic components,
Wherein the polyarylenesulfide resin is reacted with a diiodo aromatic compound, a single sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the group sulfur and the polymerization inhibitor Wherein the polyarylenesulfide resin composition is a polyarylene sulfide resin composition for surface-mounted electronic parts. The method according to claim 1,
Wherein the polyarylenesulfide resin has at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and a carboxyl group derived from the polymerization inhibitor. 3. The method according to claim 1 or 2,
Wherein the polyarylenesulfide resin has a 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. 4. The method according to any one of claims 1 to 3,
Wherein the polyarylenesulfide resin has a nonylenon index of 0.95 to 1.75 at 300 DEG C and 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. A molded article for surface-mounted electronic parts obtained by molding the polyarylenesulfide resin composition according to any one of claims 1 to 4. A molded product according to claim 5, and a surface-mounted electronic component having a metal terminal.