JP7257855B2 - Polyarylene sulfide resin composition, molded article thereof, and surface mount electronic component - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition, a molded product thereof, and a surface mount electronic component.

In recent years, in the field of the electrical and electronic industry, along with the miniaturization of products and the improvement of productivity, the surface mount method (hereinafter abbreviated as "SMT method") is sometimes used to mount resin-based electronic components on printed circuit boards. ) has shifted to a surface mounting method called Conventionally, tin-lead eutectic solder (melting point: 184°C) was commonly used as the technology for mounting electronic components on substrates using this SMT method. A lead-free solder with several metals added to the base is used.

Such lead-free solder has a higher melting point than tin-lead eutectic solder. For example, tin-silver eutectic solder has a melting point of 220°C. The temperature had to be increased further. Therefore, when soldering a resin-based electronic component such as a connector, there is a problem that the electronic component is melted or deformed in a heating furnace (reflow furnace). Therefore, there has been a strong demand for resin materials with high heat resistance for use in surface-mounted electronic components.

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 highly heat-resistant resin material. It is proposed that a surface mount electronic component comprising a molded article of a resin composition containing the polyarylene sulfide resin and a metal terminal is melted or deformed even in a heating furnace (reflow furnace). can be suppressed (see Patent Document 1, for example).

WO2009/096401

However, a conventional composition containing a polyarylene sulfide resin generates a relatively large amount of gas when heated during molding, which may corrode metal terminals of electronic parts. In addition, conventional polyarylene sulfide resin compositions or molded articles thereof still have room for improvement in properties such as mechanical strength, metal adhesion, and cavity balance.

Therefore, the problem to be solved by the present invention is to prevent melting or deformation of surface-mounted electronic components in a heating furnace (reflow furnace), and to suppress the amount of gas generated by heating, and furthermore, a resin composition or A polyarylene sulfide resin composition, a molded article using the resin composition, and a surface mount electronic component comprising the molded article, which have excellent mechanical strength, metal adhesion, and cavity balance characteristics in the molded article to provide.

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

That is, the present invention provides at least one selected from the group consisting of polyarylene sulfide resins, inorganic fillers, thermoplastic resins other than polyarylene sulfide resins, elastomers, and crosslinkable resins having two or more crosslinkable functional groups. A polyarylene sulfide resin composition for surface mount electronic components, wherein the polyarylene sulfide resin comprises a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and a diiodo aromatic compound. The present invention relates to a polyarylene sulfide resin composition for surface mount electronic components, obtainable by a process comprising reacting a group compound, elemental sulfur and a polymerization inhibitor in a molten mixture.

According to the present invention, it is possible to prevent the melting or deformation of surface-mounted electronic components in a heating furnace (reflow furnace) and suppress the amount of gas generated by heating, and furthermore, the resin composition or its molded product is excellent. The object of the present invention is to provide a polyarylene sulfide resin composition, a molded product using the resin composition, and a surface mount electronic component comprising the molded product, which have excellent mechanical strength, metal adhesion, and cavity balance characteristics.

Incidentally, the cavity balance relates to the uniformity of the degree of filling 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 balance of the molding material is not sufficient, there is a tendency for defective molding to occur such that some of the cavities are not sufficiently filled.

Preferred embodiments of the present invention are described in detail below. However, the present invention is not limited to the following embodiments.

The polyarylene sulfide resin used in the present embodiment is obtained by reacting a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor. can be obtained by a method comprising According to such a 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 diiodoaromatic compound has an aromatic ring and two iodine atoms directly attached to the aromatic ring. Diiodoaromatic compounds include, but are not limited to, diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenylether, and diiododiphenylsulfone. The substitution positions of the two iodine atoms are not particularly limited, but it is preferable that the two substitution positions are located as far apart as possible in the molecule. Preferred substitution positions are the para and 4,4'-positions.

The aromatic ring of the diiodo aromatic compound includes 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 an arylketone. may be substituted with at least one substituent selected from 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. , more preferably in the range of 0.001 to 1% by mass.

Elemental sulfur means a substance composed only of sulfur atoms (S ₈ , S ₆ , S ₄ , S _{2 ,} etc.), and its form is not limited. Specifically, elemental sulfur that is commercially available as a drug under local law may be used, or a mixture containing _S8 , _S6, etc. that is commonly available may be used. The purity of elemental sulfur is also not particularly limited. Elemental sulfur may be in the form of granules or powder 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, and even 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 that inhibits or terminates the polymerization reaction in the polymerization reaction of the polyarylene sulfide resin. 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 carboxyl group and a salt of a carboxyl group to the end of the main chain of the polyarylene sulfide resin. That is, the polymerization inhibitor is preferably a compound having one or more at least one group selected from the group consisting of hydroxy groups, amino groups, carboxyl groups and salts of carboxyl groups. Moreover, the polymerization inhibitor may have the above functional group, or the above functional group may be generated by a polymerization termination reaction or the like.

As a 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 a polymerization inhibitor.

一般式（１）で表される化合物によれば、下記式（１－１）で表される一価の基が主鎖の末端基として導入される。式（１－１）中のＹは、重合禁止剤に由来するヒドロキシ基、アミノ基等である。

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

一般式（２）で表される化合物によれば、下記式（２－１）で表される一価の基が主鎖の末端基として導入される。一般式（１）で表される化合物に由来するヒドロキシ基が、例えば、式（２）中のカルボニル基の炭素原子と硫黄ラジカルと結合することによりポリアリーレンスルフィド樹脂中に導入され得る。

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

式（１－１）又は（２－１）で表される基は、ポリアリーレンスルフィド樹脂の主鎖中に原料（単体硫黄）に由来して存在するジスルフィド結合が溶融温度下でラジカル開裂して発生した硫黄ラジカルと、一般式（１）で表される化合物又は一般式（２）で表される化合物とが結合することによって、ポリアリーレンスルフィド樹脂中に導入されると考えられる。これら特定構造の構成単位の存在は、一般式（１）又は（２）で表される化合物を用いた溶融重合により得られたポリアリーレンスルフィド樹脂に特徴的である。

The group represented by formula (1-1) or (2-1) is formed by radical cleavage of the disulfide bond present in the main chain of the polyarylene sulfide resin originating from the starting material (monolithic sulfur) at the melting temperature. It is believed that the generated sulfur radicals are combined with the compound represented by the general formula (1) or the compound represented by the general formula (2) to be introduced into the polyarylene sulfide resin. The presence of structural units having these specific structures is characteristic of polyarylene sulfide resins obtained by melt polymerization using compounds represented by general formula (1) or (2).

Examples of compounds represented by general formula (1) include 2-iodophenol and 2-aminoaniline. Examples of compounds represented by general formula (2) include 2-iodobenzophenone.

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

一般式（３）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、又は、下記一般式（ａ）、（ｂ）若しくは（ｃ）で表される一価の基を表し、Ｒ^１又はＲ^２の少なくともいずれか一方は一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基である。一般式（４）中、Ｚは、ヨウ素原子又はメルカプト基を表し、Ｒ^３は、下記一般式（ａ）、（ｂ）又は（ｃ）で表される一価を表す。一般式（５）中、Ｒ^４は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。

In general 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 one of R ² 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 represented by general formula (a), (b) or (c) below. In general formula (5), ^R4 represents a monovalent group represented by general formula (a), (b) or (c).

一般式（ａ）～（ｃ）中のＸは、水素原子又はアルカリ金属原子であるが、反応性が良好となる点から水素原子が好ましい。アルカリ金属原子としては、ナトリウム、リチウム、カリウム、ルビジウム、及びセシウムなどが挙げられるが、ナトリウムが好ましい。一般式（ｂ）中、Ｒ^１０は炭素原子数１～６のアルキル基を表す。一般式（ｃ）中、Ｒ^１１は水素原子又は炭素原子数１～３のアルキル基を表し、Ｒ^１２は炭素原子数１～５のアルキル基を表す。

X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom, preferably a hydrogen atom from the viewpoint of good reactivity. Alkali metal atoms include sodium, lithium, potassium, rubidium, and cesium, with sodium being preferred. In general formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In general formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms.

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

（式中、Ｒ^５は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。）

(Wherein, ^R5 represents a monovalent group represented by general formula (a), (b) or (c).)

（式中、Ｒ^６は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。）

(Wherein, ^R6 represents a monovalent group represented by general formula (a), (b) or (c).)

A compound having no functional group such as a carboxyl group may be used as the polymerization inhibitor. Examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, 2 At least one compound selected from -(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 melt polymerization in a melt mixture obtained by heating a mixture containing a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and optionally a catalyst. Generate. The ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 mol, more preferably in the range of 0.8 to 1.2 mol, per 1 mol of elemental sulfur. Further, the ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mol, more preferably in the range of 0.0005 to 0.05 mol, per 1 mol of solid sulfur. .

The timing of adding the polymerization inhibitor is not particularly limited, but the mixture containing the diiodo aromatic compound, elemental sulfur and optionally added catalyst is heated so that the temperature of the mixture is preferably 200° C. to 320° C. When the temperature reaches the range, more preferably 250 to 320° C., the polymerization inhibitor can be added.

A nitro compound can be added to the molten mixture as a catalyst to control the rate of polymerization. Various nitrobenzene derivatives can be used as the nitro compound. Nitrobenzene derivatives include, for example, 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diiodo-4-nitroamine. The amount of the catalyst may be the amount normally added as a catalyst, and for example, it is preferably in the range of 0.01 to 20 parts by weight per 100 parts by weight of elemental sulfur.

Conditions for the melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably 175°C or higher and the melting point of the polyarylene sulfide resin to be produced plus 100°C or lower, more preferably 180 to 350°C. The 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 need not be constant. For example, at 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], and then continuously or Polymerization is carried out while increasing the temperature and reducing the pressure 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., Moreover, the polymerization can be carried out with the absolute pressure in the range of 1 [cPa] to 6 [kPa]. As used herein, the melting point of a resin means a value measured according to JIS K 7121 using a differential scanning calorimeter (DSC device Pyris Diamond manufactured by Perkin Elmer).

From the viewpoint of obtaining a high degree of polymerization while preventing an oxidative cross-linking reaction, the melt polymerization is preferably carried out in a non-oxidizing atmosphere. In a non-oxidizing atmosphere, the oxygen concentration in 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, and even 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.

Melt polymerization can be carried out using, for example, a melt kneader equipped with a heating device, a pressure reducing device and a stirring device. Melt-kneaders include, for example, Banbury mixers, kneaders, continuous kneaders, single-screw extruders and twin-screw extruders.

The melt mixture for melt polymerization is preferably substantially free of solvent. More specifically, the amount of solvent contained in the molten mixture is preferably 10 parts by mass with respect to a total of 100 parts by mass of the diiodo aromatic compound, simple sulfur, polymerization inhibitor, and optionally catalyst. part or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. The amount of solvent may range from 0 parts by weight or more, from 0.01 parts by weight or more, or from 0.1 parts by weight or more.

After cooling the molten mixture (reaction product) after melt polymerization to obtain a mixture in a solid state, the mixture is heated under reduced pressure or under atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. good too. As a result, not only can the molecular weight be further increased, but also the generated iodine molecules are removed by sublimation, so that the concentration of iodine atoms in the polyarylene sulfide resin can be kept low. 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 even more preferably in the range of 150 to 230°C, a solid mixture can be obtained. Heating after cooling to the solid state can be carried out under the same temperature and pressure conditions as melt polymerization.

The reaction product containing the polyarylene sulfide resin obtained by the melt polymerization step can be directly charged into a melt kneader as it is for producing a resin composition. Adding a solvent in which the reaction product dissolves to prepare a melt, and removing the reaction product from the reaction apparatus in the state of the melt is preferable because not only the productivity is excellent but also the reactivity is good. 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 the latter stage of the melt polymerization reaction, and as described above, the molten mixture (reaction product) is cooled to obtain a solid state. After obtaining the mixture, the mixture is heated under pressure, under reduced pressure, or under atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. The step of preparing the melt may be performed in a non-oxidizing atmosphere. Further, the temperature for heating and dissolving may be in the range of the melting point or higher of the solvent in which the reaction product is dissolved, preferably in the range of 200 to 350 ° C., more preferably in the range of 210 to 250 ° C., under pressure. It is preferable to use

The blending ratio of the solvent in which the reaction product is dissolved, which is used to prepare the dissolved product, is 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. It is preferably 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 Phillips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinoic acid, and ε-caprolactam. , N-methyl-ε-caprolactam and other aliphatic cyclic amide compounds, hexamethylphosphoric acid triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA) and other amide compounds, polyethylene Etherified polyethylene glycol compounds such as glycol dialkyl ether (having a degree of polymerization of 2000 or less and having an alkyl group having 1 to 20 carbon atoms), and sulfoxide compounds such as tetramethylene sulfoxide and dimethyl sulfoxide (DMSO). be done. Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4′-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 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-pyrrolidinone, 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, diphenylcarbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxy naphthalene, 4-bromodiphenyl ether, pyrene, 9,9'-bi-fluorene, 4,4'-isopropyllidene-diphenol, epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalate, diphenyl-terphthalate and One or more solvents selected from the group consisting of 1-chloronaphthalene can be used.

It is preferable to prepare the resin composition by melt-kneading the melt taken out from the reaction apparatus with the other components after post-treatment, since the reactivity becomes better. The post-treatment method of the dissolved material is not particularly limited, and includes, for example, the following methods.
(1) The dissolved substance 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 matter after the solvent distillation is water, and the solvent used for the dissolved substance (or an organic solvent having a similar solubility to the low molecular weight polymer), washing once or twice with a solvent selected from acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtration and drying.
(2) Solvents such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons (soluble in the solvent of the melt and at least polyarylene A solvent which is a poor solvent for sulfide resins) is added as a precipitant to precipitate solid products containing polyarylene sulfide resins, inorganic salts, etc., and the solid products are separated by filtration, washed and dried. Method.
(3) After adding the solvent (or an organic solvent having an equivalent solubility to the low-molecular-weight polymer) used in the dissolution to the dissolution and stirring, filtering to remove the low-molecular-weight polymer, A method of washing once or twice or more with a solvent selected from water, acetone, methyl ethyl ketone, alcohol, etc., followed by neutralization, washing with water, filtration and drying.

In the post-treatment methods exemplified in (1) to (3) above, the drying of the polyarylene sulfide resin may be carried out in a vacuum, in the air, or in an atmosphere of an inert gas such as nitrogen. may The polyarylene sulfide resin can also 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.

A reaction in which a polyarylene sulfide resin is produced by melt polymerization is exemplified below.

反応式（１）～（５）は、例えば一般式（ａ）、（ｂ）又は（ｃ）で表される基を含む置換基Ｒを有するジフェニルジスルフィドを重合禁止剤として用いた場合の、ポリフェニレンスルフィドが生成する反応の例である。反応式（１）は、重合禁止剤中の－Ｓ－Ｓ－結合が、溶融温度下でラジカル開裂する反応である。反応式（２）は、反応式（１）で発生した硫黄ラジカルが成長中の主鎖の末端ヨウ素原子の隣接炭素原子を攻撃し、ヨウ素原子が脱離することで、重合が停止するとともに、主鎖の末端に置換基Ｒが導入される反応である。反応式（３）は、ポリアリーレンスルフィド樹脂の主鎖中に原料（単体硫黄）に由来して存在するジスルフィド結合が溶融温度下でラジカル開裂する反応である。反応式（４）は、反応式（３）で発生した硫黄ラジカルと、反応式（１）で発生した硫黄ラジカルとの再結合によって、重合が停止するとともに、置換基Ｒが主鎖の末端に導入される反応である。脱離したヨウ素原子は遊離状態（ヨウ素ラジカル）にあるか、又は、反応式（５）のようにヨウ素ラジカル同士が再結合することで、ヨウ素分子が生成する。

Reaction formulas (1) to (5) show, for example, polyphenylene when diphenyl disulfide 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 produces a sulfide. Reaction formula (1) is a reaction in which the —S—S— bond in the polymerization inhibitor is radically cleaved at the melting temperature. In reaction formula (2), the sulfur radical generated in reaction formula (1) attacks the carbon atom adjacent to the terminal iodine atom of the growing main chain, and the iodine atom is eliminated, thereby terminating polymerization and This is a reaction in which a substituent R is introduced at the end of the main chain. Reaction formula (3) is a reaction in which a disulfide bond present in the main chain of the polyarylene sulfide resin originating from the starting material (monolithic sulfur) is radically cleaved at the melting temperature. In Reaction Formula (4), the recombination of the sulfur radicals generated in Reaction Formula (3) and the sulfur radicals generated in Reaction Formula (1) terminates the polymerization, and the substituent R is at the end of the main chain. It is the reaction that is introduced. The released iodine atoms are in a free state (iodine radicals), or iodine molecules are generated by recombination of iodine radicals as in reaction formula (5).

A reaction product containing a polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from raw materials. Therefore, polyarylene sulfide resins are usually used in the form of mixtures containing iodine atoms for the preparation of spinning resin compositions. The concentration of iodine atoms in the mixture is, for example, in the range of 0.01-10000 ppm, preferably in the range of 10-5000 ppm, relative to the polyarylene sulfide resin. It is possible to keep the iodine atom concentration low by utilizing the sublimation property of iodine molecules. is. Furthermore, although it is possible to remove iodine atoms below the detection limit, it is not practical in terms of productivity. The detection limit is, for example, about 0.01 ppm. The polyarylene sulfide resin of the present embodiment obtained by melt polymerization or a reaction product containing the same contains iodine atoms. It can be clearly distinguished from legally obtained polyarylene sulfide.

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

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

で表される繰り返し単位（アリーレンスルフィド単位）を含む主鎖を有する。式（１０）で表される繰り返し単位は、パラ位で結合する下記式（１０ａ）：

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

で表される繰り返し単位、及び、メタ位で結合する下記式（１０ｂ）：

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

で表される繰り返し単位であることがより好ましい。これらの中でも、式（１０ａ）で表されるパラ位で結合した繰り返し単位が、樹脂の耐熱性及び結晶性の面で好ましい。

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

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

（式中、Ｒ^２０及びＲ^２１は、それぞれ独立に水素原子、炭素原子数１～４のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、又はエトキシ基を表す。）で表される、芳香族環に結合した側鎖としての置換基を有する繰り返し単位を含み得る。ただし、結晶化度及び耐熱性の低下の観点から、ポリフェニレンスルフィド樹脂は、一般式（１１）の繰り返し単位を実質的に含まないことが好ましい。より具体的には、式（１１）で表される繰り返し単位の割合は、式（１０）で表される繰り返し単位と式（１１）で表される繰り返し単位との合計に対して、好ましくは２質量％以下、より好ましくは０．２質量％以下である。

(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). , may contain repeat units having substituents as side chains attached to the aromatic ring. However, from the viewpoint of reduction in crystallinity and heat resistance, the polyphenylene sulfide resin preferably does not substantially contain the repeating unit of general formula (11). More specifically, the proportion of the repeating unit represented by formula (11) is preferably It is 2% by mass or less, more preferably 0.2% by mass or less.

The polyarylene sulfide resin of the present embodiment is mainly composed of the above arylene sulfide units, but is usually derived from elemental sulfur of the raw material, represented by the following formula (20):

で表されるジスルフィド結合に係る構成単位も主鎖中に含む。耐熱性、機械的強度の点から、式（２０）で表される構成単位の割合は、アリーレンスルフィド単位と、式（２０）で表される構成部位との合計に対して、好ましくは２．９質量％以下の範囲、より好ましくは１．２質量％以下の範囲である。ポリアリーレンスルフィド樹脂が式（２０）で表される構成単位を含むことによって、ポリアリーレンスルフィド樹脂組成物と金属との密着性が向上する点で好ましい。

The main chain also contains a structural unit related to a disulfide bond represented by . From the viewpoint of heat resistance and mechanical strength, the ratio of the structural unit represented by formula (20) is preferably 2.0 to the total of the arylene sulfide unit and the structural site represented by formula (20). The range is 9% by mass or less, more preferably 1.2% by mass or less. Including the structural unit represented by formula (20) in the polyarylene sulfide resin is preferable in that the adhesion between the polyarylene sulfide resin composition and the metal is improved.

Mw/Mtop of the polyarylene sulfide resin according to this embodiment is preferably in the range of 0.80 to 1.70, more preferably in the range of 0.90 to 1.30. By setting Mw/Mtop within such a range, the processability of the polyarylene sulfide resin can be improved, and good cavity balance can be imparted. In the present specification, Mw indicates the weight average molecular weight measured by gel permeation chromatography, and Mtop indicates the average molecular weight (peak molecular weight) at which the detection intensity of the chromatogram obtained by the same measurement becomes maximum. Mw/Mtop indicates the molecular weight distribution of the object to be measured. Generally, when this value is close to 1, the molecular weight distribution is narrow, and as this value increases, the molecular weight distribution is broad. The measurement conditions for gel permeation chromatography are the same as those used 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 polyarylene sulfide resin according to the present embodiment is not particularly limited as long as it does not impair the effects of the present invention, but the lower limit is 28,000 or more from the viewpoint of excellent mechanical strength. is preferred, and a range of 30,000 or more is more preferred. 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, furthermore 55,000 or less, from the viewpoint of being able to impart a better cavity balance. is most preferred. Furthermore, from the viewpoint of being able to impart good cavity balance while having excellent mechanical strength, a polyarylene sulfide resin in the range of 28,000 to 60,000, more preferably in the range of 30,000 to 55,000 A polyarylene sulfide resin having a weight average molecular weight in the range of more than 60,000 to 100,000 or less may be used with the polyarylene sulfide resin.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95-1.75, more preferably in the range of 1.0-1.70. By setting the non-Newtonian exponent within such a range, the processability of the polyarylene sulfide resin can be improved, and good cavity balance can be imparted. As used herein, the non-Newtonian index refers to an index that satisfies the following relational expression between shear rate and shear stress at a temperature of 300°C. The non-Newtonian index can be an index related to the molecular weight of the object to be measured or the molecular structure such as linear, branched, or crosslinked. As the value increases, it indicates that more branches and cross-linked structures are included.
D=α× ^Sn
(In the above formula, D represents shear rate, S represents shear stress, α represents a constant, and n represents a non-Newtonian exponent.)

A polyarylene sulfide resin having Mw/Mtop and a non-Newtonian index within the specific ranges described above can be obtained, for example, by combining a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor with a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor. can be obtained by increasing the molecular weight of such polyarylene sulfide resin to some extent in a method of reacting (solution polymerization) in a molten mixture containing

The melting point of the polyarylene sulfide resin according to the present embodiment is preferably in the range of 250-300°C, more preferably in the range of 265-300°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 a ratio of the orifice length to the orifice diameter (orifice length/orifice diameter) of 10/1. means the melt viscosity after holding for 6 minutes at

The polyarylene sulfide resin composition according to this embodiment can contain one or more inorganic fillers. By blending the inorganic filler, a composition with high rigidity and high heat resistance stability can be 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, and glass fibers. , fibrous fillers such as carbon fibers and wollastonite fibers, and glass flakes. It is particularly preferred 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, still more preferably 15 to 150 parts by mass, with respect to 100 parts by mass of the polyarylene sulfide resin. It is in the range of parts by mass. When the content of the inorganic filler is within these ranges, a superior effect can be obtained in terms of maintaining the mechanical strength of the molded product.

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

Thermoplastic resins blended in the polyarylene sulfide resin composition include, for example, polyesters, polyamides, polyimides, polyetherimides, polycarbonates, polyphenylene ethers, polysulfones, polyethersulfones, polyetheretherketones, polyetherketones, and polyethylenes. , polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (such as liquid crystal polyester).

Polyamides are polymers with amide linkages (--NHCO--). Examples of polyamide resins include (i) a polymer obtained by polycondensation of diamine and dicarboxylic acid, (ii) a polymer obtained by polycondensation of aminocarboxylic acid, and (iii) a polymer obtained by ring-opening polymerization of lactam. is mentioned. Polyamide can be used individually or in combination of 2 or more types.

Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As the aliphatic diamine, straight-chain diamines or diamines having 3 to 18 carbon atoms having side chains are preferred. 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-dodecamethylene Diamine, 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 the aromatic diamine, a diamine having 6 to 27 carbon atoms and having a phenylene group is preferred. 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'-diaminodiphenylsulfide, 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-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4 -bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4 ,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethylbenzidine may be mentioned.
These can be used individually or in combination of 2 or more types.

As the alicyclic diamine, a diamine having 4 to 15 carbon atoms and having a cyclohexylene group is preferred. Examples of suitable alicyclic diamines include 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 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.

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 preferred. 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, placylic acid, tetradecane. Diacids, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can be used individually or in combination of 2 or more types.

As the aromatic dicarboxylic acid, a dicarboxylic acid having 8 to 15 carbon atoms and having a phenylene group is preferred. Examples of suitable 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. acids, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. . These can be used individually or in combination of 2 or more types. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can also be used within the range that can be melt-molded.

As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferred. 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.

Lactams from which polyamides are derived include, for example, ε-caprolactam, ω-laurolactam, ζ-enantholactam, and η-capryllactam. These can be used individually or in combination of 2 or more types.

Preferred polyamide raw material combinations include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine/adipic acid (nylon 6,6), and 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 acids, 1,9-nonamethylenediamine/terephthalic acid/ε-caprolactam, 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid, and m-xylylenediamine/adipic acid. be done. Among these, 1,4-tetramethylenediamine/adipic acid (nylon 4,6), 1,6-hexamethylenediamine/terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, 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 is 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 5 to 45 parts by mass, relative to 100 parts by mass of the polyarylene sulfide resin. It is in the range of parts by mass. By setting the content of the thermoplastic resin other than the polyarylene sulfide resin within these ranges, the effect of further improving heat resistance, chemical resistance and mechanical properties can be obtained.

A thermoplastic elastomer is often used as the elastomer to be blended in the polyarylene sulfide resin composition. Thermoplastic elastomers include, for example, polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In this specification, thermoplastic elastomers are classified as elastomers, not as thermoplastic resins.

Elastomers (particularly thermoplastic elastomers) preferably have functional groups capable of reacting with at least one group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups and salts of carboxyl groups. Thereby, it is possible to obtain a resin composition which is particularly excellent in terms of adhesiveness, impact resistance, etc., and which can suppress the amount of gas generated by heating. Such functional groups include epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, isocyanate group, oxazoline group, and formula: R (CO) O (CO) - or R (CO) O - (in the formula, R represents an alkyl group having 1 to 8 carbon atoms.). A thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an α-olefin and a vinyl polymerizable compound having the functional group. Examples of α-olefins include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having the functional group include α,β-unsaturated carboxylic acids and their alkyl esters such as (meth)acrylic acid and (meth)acrylic acid esters, maleic acid, fumaric acid, itaconic acid and Other examples include α,β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters, acid anhydrides thereof, etc.), glycidyl (meth)acrylate, and the like. Among these, an epoxy group, a carboxyl group, and a formula: R (CO) O (CO) - or R (CO) O - (wherein R represents an alkyl group having 1 to 8 carbon atoms) Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the groups represented are preferred from the standpoint of improving toughness and impact resistance.

The content of the elastomer varies depending on its type and application, and cannot be generally defined. The range is from 100 parts by mass to 100 parts by mass, preferably from 5 to 45 parts by mass. When the content of the elastomer is within these ranges, a more excellent effect can be obtained in terms of ensuring 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 crosslinkable functional groups include epoxy groups, phenolic hydroxyl groups, amino groups, amide groups, carboxyl groups, acid anhydride groups, and isocyanate groups. Examples of crosslinkable resins include epoxy resins, phenolic resins, and urethane resins.

As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group, a hydroxyl group, or the like. Examples of suitable aromatic epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak. type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, and biphenyl novolac type epoxy resins. These aromatic epoxy resins can be used alone or in combination of two or more. Among these aromatic epoxy resins, novolac epoxy resins are preferred, and cresol novolak epoxy resins are more preferred, in view of their 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, relative to 100 parts by mass of the polyarylene sulfide resin. It is in the range of parts by mass. When the content of the crosslinkable resin is within these ranges, the effect of improving the rigidity and heat resistance of the molded article can be obtained particularly remarkably.

The polyarylene sulfide resin composition can contain a silane compound having a functional group capable of reacting with at least one group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups and salts of carboxyl groups. As a result, it is possible to obtain a resin composition in which the compatibility between the polyarylene sulfide resin and other components is improved and the amount of gas generated by heating can be suppressed. Such silane compounds include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyl Silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane are included.

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 with respect to 100 parts by mass of the polyarylene sulfide resin. . When the content of the silane compound is within these ranges, the effect of improving the compatibility between the polyarylene sulfide resin and the other components is obtained.

The polyarylene sulfide resin composition according to the present mode of practice may contain other additives such as release agents, colorants, heat stabilizers, UV stabilizers, foaming agents, rust inhibitors, flame retardants and lubricants. good. The content of the additive is preferably, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin.

The polyarylene sulfide resin composition can be obtained, for example, in the form of a pellet-like compound or the like, by melt-kneading the polyarylene sulfide resin obtained by the above method and the other components. The melt-kneading temperature is, for example, preferably in the range of 250 to 350°C, 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 other materials such as the above components, can be processed by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. It can be processed into molded products with excellent moldability, dimensional stability, and the like. Since the polyarylene sulfide resin composition according to the present embodiment generates a small amount of gas when heated, it enables easy production of high-quality molded articles.

The molded article obtained in this manner is suitably used for surface-mounted electronic components. A surface-mounted electronic component is composed of, for example, a molded product of a polyarylene sulfide resin composition and metal terminals, and is fixed on a printed wiring board or circuit board by a surface-mounting method. be. In order to fix the electronic component to the substrate by the surface mounting method, the electronic component is placed on the surface of the substrate so that the metal terminals of the electronic component are in contact with the current-carrying parts on the substrate via the solder balls, and then heated in the reflow furnace by the above-described heating method. A method of soldering the electronic component to the board by heating at a temperature of . Specific examples of such surface-mounted electronic components include connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, housings for ICs and LEDs, etc. for surface-mounting systems. .

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

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.

1. Evaluation method [bending properties]
・Compliant test method: ASTM D-790
・Test piece: 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (length)
・Test results: Average value of n = 10 tests

[Hot water resistance]
The test piece was immersed in hot water at 95° C., and the change in bending strength over time was examined.
・Test piece: 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (length)
・Bending strength test method: ASTM D-790
・Evaluation item: retention rate of bending strength after 1000 hours and 3000 hours with respect to initial strength ・Test results: average value of n = 5 tests

[Metal adhesion strength]
A metal piece (SUS304) of 4 x 10 x 49 mm set in a mold was injected with a polyarylene sulfide resin composition of the same size and molded. was carried out, and the metal adhesion strength was measured.

[Cavity balance]
Using a washer mold with 40 cavities, the PPS compound was injection molded under the lowest molding conditions as long as the cavity (C1) closest to the primary sprue was completely filled. 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.

After molding, the filling degree of cavity (C1) and the cavity furthest from the primary sprue (C10) on the same runner were 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), the better the cavity balance. Based on the degree of filling, the cavity balance of each composition was judged 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% by mass or less

[Gas generation amount]
Using a gas chromatograph mass spectrometer, a predetermined amount of a sample of the 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 heat resistance]
Pellets of the resin composition were molded using an injection molding machine to form a box-shaped connector measuring 70 mm long, 10 mm wide, 8 mm high, and 0.8 mm thick. Then, this box-shaped connector was placed on a printed circuit board and heated under the following reflow conditions. After heating, the box-shaped connector was visually observed, and the appearance was evaluated according to the following two-step criteria.
O: No change in appearance.
x: Blistering or melting was observed.
(reflow conditions)
Reflow heating was performed with an infrared reflow device (“TPF-2” manufactured by Asahi Engineering Co., Ltd.). As for the heating conditions at this time, after preheating at 180° C. for 100 seconds, the heating was maintained until the surface of the substrate reached 280° C. That is, the temperature profile (temperature curve) is set to 100 seconds at 200°C or higher, 90 seconds at 220°C or higher, 80 seconds at 240°C or higher, and 60 seconds at 260°C or higher. was set, and the heating was held.

2. Synthesis of polyphenylene sulfide resin (PPS resin) (Synthesis Example 1: Synthesis of PPS-1)
p-diiodobenzene (Tokyo Kasei Co., Ltd., p-diiodobenzene purity 98.0% or more) 300.0 g, solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) 27.00 g, 4,4'- 2.0 g of dithiobisbenzoic acid (4,4′-dithiobisbenzoic acid, technical grade, manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 180° C. and 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 subjected to melt polymerization for 8 hours while changing the temperature and pressure stepwise so that the absolute pressure was 133 Pa at 320°C. After completion of the reaction, 200 g of NMP was added, the mixture was heated and stirred at 220° C., and the resulting dissolved matter was filtered. 320 g of NMP was added to the dissolved matter after filtration, and the cake was washed and filtered. 1 L of ion-exchanged water was added to the obtained cake containing NMP, and the mixture was stirred in an autoclave at 200° C. for 10 minutes. Next, the cake was filtered, and 1 L of deionized water at 70° C. was added to the filtered cake to wash the cake. 1 L of ion-exchanged water was added to the resulting water-containing cake, and the mixture was stirred for 10 minutes. Next, the cake was filtered, and 1 L of deionized water at 70° C. was added to the filtered cake to wash the cake. After repeating this operation once more, 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 a PPS resin (PPS-2) was obtained in the same manner as in Synthesis Example 1 except that "2-iodoaniline (manufactured by Tokyo Kasei Co., Ltd.)" was used instead of "4,4'-dithiobisbenzoic acid". rice field.

(Synthesis Example 3: Synthesis of PPS-3)
91 g of a 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)
A 2 L autoclave was charged with 600 g of N-methylpyrrolidone and 336.3 g (2.0 mol) of sodium sulfide pentahydrate, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Then, 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 to the system, and the mixture was heated at 220° C. for 5 hours. and further reacted at 240° C. for 2 hours under a nitrogen atmosphere. After cooling, the contents of the reaction vessel were taken out, a portion was sampled, and unreacted 2,5-dichloroaniline was quantified by gas chromatography. The remaining slurry was washed with hot water several times and the polymer cake was filtered off. The cake was dried at 80° C. under reduced pressure 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.

３．ポリフェニレンスルフィド樹脂組成物（ＰＰＳコンパウンド）
［原料］
ＰＰＳ樹脂組成物を調製するため、以下の材料を準備した。
（熱可塑性樹脂）
ＰＡ６Ｔ：テレフタル酸６５モル％、イソフタル酸２５モル％、アジピン酸１０モル％を必須の単量体成分として反応させて得られた芳香族ポリアミド（融点３１０℃、Ｔｇ１２０℃）
ＰＡ９Ｔ：ノナンジアミンとテレフタル酸とを反応させて得られたポリアミド（株式会社クラレ製、「ジェネスタ Ｎ１０００Ａ」）
ＰＡ４６：ポリアミド４６（ディーエスエム ジャパン エンジニアリング プラスチックス株式会社製、「スタニール ＴＳ３００」）
（無機質充填剤）
ＧＦ:ガラス繊維チョップドストランド（繊維径１０μｍ、長さ３ｍｍ）

3. Polyphenylene sulfide resin composition (PPS compound)
[material]
The following materials were prepared to prepare the PPS resin composition.
(Thermoplastic resin)
PA6T: Aromatic polyamide obtained by reacting 65 mol% terephthalic acid, 25 mol% isophthalic acid, and 10 mol% adipic acid as essential monomer components (melting point 310°C, Tg 120°C)
PA9T: Polyamide obtained by reacting nonanediamine and terephthalic acid (manufactured by Kuraray Co., Ltd., "Genestar N1000A")
PA46: Polyamide 46 (manufactured by DM Japan Engineering Plastics Co., Ltd., "Stanyl TS300")
(Inorganic filler)
GF: glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

[Preparation and evaluation of compound]
After uniformly mixing each raw material with the formulation shown in Table 1 with a tumbler, the mixture was melt-kneaded at 300° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine) to obtain a compound in the form of pellets. The resulting compound was injection molded under the conditions of a cylinder temperature of 300°C and a mold temperature of 140°C to prepare test specimens for bending characteristics, metal adhesion strength, cavity balance and hot water resistance tests, and various evaluations were performed. . In addition, the amount of gas generated was measured for the PPS resin alone and the compound. Table 2 shows the evaluation results.

表２に示される結果から明らかなように、ＰＰＳ－１、ＰＰＳ－２及びＰＰＳ－３は、機械特性（曲げ強さ、曲げ破断伸び）、金属密着強さ、キャビティーバランス、耐熱水性、ガス発生量の点で、ＰＰＳ－４よりも優れていた。

As is clear from the results shown in Table 2, PPS-1, PPS-2 and PPS-3 have mechanical properties (flexural strength, bending elongation at break), metal adhesion strength, cavity balance, hot water resistance, gas It was superior to PPS-4 in terms of generated amount.

Claims (13)

a polyarylene sulfide resin;
At least one other component selected from the group consisting of 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 mount electronic components containing
The polyarylene sulfide resin is obtained by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibitor. can be obtained,
The polyarylene sulfide resin has at least one group selected from the group consisting of a carboxyl group derived from the polymerization inhibitor and a salt of the carboxyl group;
the polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70, wherein the Mw and Mtop are the weight average molecular weight and peak molecular weight, respectively, measured by gel permeation chromatography;
The other component is 1 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin,
The surface mount electronic component comprises a molded article obtained by molding a polyarylene sulfide resin composition, and a metal terminal.
A polyarylene sulfide resin composition for surface mount electronic parts. The polyarylene sulfide resin is
The following general formula (20) in the main chain

2. The surface-mounted electronic device according to claim 1, which is a mixture containing a polyarylene sulfide resin having disulfide bonds represented by and iodine atoms at a ratio of 0.01 to 10,000 ppm with respect to the polyarylene sulfide resin. A polyarylene sulfide resin composition for parts. The polyarylene sulfide resin is
The following general formula (a) at the end

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 In (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. 3. The polyarylene sulfide resin composition for surface mount electronic parts according to 1 or 2. The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300° C. and a Mw/Mtop of 0.80 to 1.70;
The polyarylene sulfide resin composition for surface mount electronic parts according to any one of claims 1 to 3 , wherein said Mw and Mtop are respectively a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography. The polyarylene sulfide resin composition for surface mount electronic parts according to any one of claims 1 to 4 , which is in the form of pellets. A molded product for surface mount electronic parts, obtained by molding the polyarylene sulfide resin composition according to any one of claims 1 to 5 . A surface-mounted electronic component comprising the molded article for surface-mounted electronic component according to claim 6 and a metal terminal. a polyarylene sulfide resin;
An inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and at least one other component selected from the group consisting of a crosslinkable resin having two or more crosslinkable functional groups are melt-kneaded. matter,
The polyarylene sulfide resin is obtained by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibitor. to get
The polyarylene sulfide resin has at least one group selected from the group consisting of a carboxyl group derived from the polymerization inhibitor and a salt of the carboxyl group;
the polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70, wherein the Mw and Mtop are the weight average molecular weight and peak molecular weight, respectively, measured by gel permeation chromatography;
The surface mount electronic component comprises a molded article obtained by molding a polyarylene sulfide resin composition and a metal terminal;
A method for producing a polyarylene sulfide resin composition for surface mount electronic components, characterized by: The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300° C. and a Mw/Mtop of 0.80 to 1.70;
9. The method for producing a polyarylene sulfide resin composition for surface mount electronic parts according to claim 8 , wherein said Mw and Mtop are weight average molecular weight and peak molecular weight respectively measured by gel permeation chromatography. The polymerization inhibitor has the following general formula (3), (4) or (5)

[Wherein, in general 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) , R ¹ or R ² 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 represented by general formula (a), (b) or (c) below. In general formula (5), ^R4 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 In (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. 3. The method for producing the polyarylene sulfide resin composition for surface mount electronic components according to 1 . The method for producing a polyarylene sulfide resin composition for surface mount electronic components according to any one of claims 8 to 10 , wherein the polyarylene sulfide resin composition for surface mount electronic components is in the form of pellets. Producing a polyarylene sulfide resin composition for surface mount electronic components by the production method according to any one of claims 8 to 11 , injection molding, extrusion molding, the produced polyarylene sulfide resin composition, A method for producing a molded product for surface mount electronic components, characterized by processing by one kind of melt processing method selected from the group consisting of compression molding and blow molding. A method of manufacturing a surface mount electronic component comprising a molded article and metal terminals,
soldering a surface mount electronic component comprising a molded article and metal terminals to a substrate by heating in a reflow oven;
13. A method of manufacturing a surface-mount electronic component, wherein the molded product is manufactured by the manufacturing method according to claim 12 .