JP6718232B2 - Polyarylene sulfide resin composition, molded article thereof, and surface mount electronic component - Google Patents

Description

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

2. Description of the Related Art In recent years, in the field of electric/electronic industry, a mounting method of a resin-based electronic component on a printed circuit board is sometimes referred to as a surface mounting method (hereinafter, abbreviated as “SMT method”) along with downsizing of products and improvement of productivity. ) Is called the surface mount method. Conventionally, tin-lead eutectic solder (melting point 184° C.) has been generally used as a technique for mounting electronic components on a substrate by the SMT method, but in recent years, tin has been used as an alternative material because of environmental pollution. Lead-free solder with several kinds of metals added to the base is used.

Such a lead-free solder has a higher melting point than a tin-lead eutectic solder. For example, in the case of a tin-silver eutectic solder, the melting point reaches 220° C., so that the surface of a heating furnace (reflow furnace) is used during surface mounting. The temperature had to be raised 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, a resin material having a high heat resistance has been strongly demanded for the surface mount electronic component.

On the other hand, a polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) is used as a highly heat-resistant resin material. It has been proposed to use, and a surface-mounted electronic component including a molded product of a resin composition containing the polyarylene sulfide resin and a metal terminal is melted or deformed even in a heating furnace (reflow furnace). It has been proposed that the above can be suppressed (for example, refer to Patent Document 1).

International Publication No. 2009/0964041

However, in the conventional composition containing a polyarylene sulfide resin, the amount of gas generated by heating during molding or the like is relatively large, which may corrode the metal terminals of electronic components. Further, in the conventional polyarylene sulfide resin composition or its molded product, there is still 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 the surface mounting electronic components from melting or deforming in the heating furnace (reflow furnace), and suppress the gas generation amount due to heating, and further to prevent the resin composition or In the molded product, a polyarylene sulfide resin composition having excellent mechanical strength, metal adhesion, and cavity balance characteristics, a molded product using the resin composition, and a surface mount electronic component equipped with the molded product are provided. To provide.

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

That is, the present invention is at least 1 selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition for surface-mounting electronic components, which comprises a diiodoaromatic compound, a simple sulfur, a polymerization inhibitor, and a diiodo aroma. The present invention relates to a polyarylene sulfide resin composition for surface mount electronic parts, which can be obtained by a method including reacting in a molten mixture containing a group compound, elemental sulfur and a polymerization inhibitor.

ADVANTAGE OF THE INVENTION According to this invention, while preventing a surface mounting electronic component from melting or deforming in a heating furnace (reflow furnace), the amount of gas generation by heating can be suppressed, and further, in a resin composition or its molded article, it is excellent. Another object of the present invention is to provide a polyarylene sulfide resin composition having mechanical strength, metal adhesion, and cavity balance characteristics, a molded article using the resin composition, and a surface mount electronic component including the molded article.

The cavity balance relates to the uniformity of the filling degree of each cavity when a plurality of molded products are simultaneously molded by injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is not sufficient, there is a tendency that molding defects such as insufficient filling of some cavities 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 polyarylene sulfide resin used in the present embodiment is obtained by reacting a diiodo aromatic compound, a simple substance sulfur, and a polymerization inhibitor in a melt mixture containing the diiodo aromatic compound, the simple substance sulfur, and the polymerization inhibitor. Can be obtained. According to such a method, the polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods such as the Phillips method.

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

The aromatic ring of the diiodo aromatic compound has 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 aryl sulfone and an aryl ketone. It may be substituted with at least one kind of 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. , And more preferably 0.001 to 1% by mass.

The elemental sulfur means a substance (S ₈ , S ₆ , S ₄ , S _2, etc.) composed only of sulfur atoms, and its form is not limited. Specifically, elemental sulfur that is commercially available as a local medicine may be used, or a mixture containing S ₈ and S ₆ , which is commonly available, may be used. The purity of elemental sulfur is also not particularly limited. The elemental sulfur may be in the form of particles 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 further 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 stops 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 hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group into the terminal of the main chain of the polyarylene sulfide resin. That is, the polymerization inhibitor is preferably a compound having at least one group selected from the group consisting of salts of hydroxy group, amino group, carboxyl group and carboxyl group. Further, the polymerization inhibitor may have the above-mentioned functional group, or the above-mentioned functional group may be generated by a termination reaction of the polymerization or the like.

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

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), 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 hydroxy group, an amino group or the like derived from the 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), 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 polyarylene sulfide resin by, for example, binding to the carbon atom of the carbonyl group in the formula (2) and 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 the formula (1-1) or (2-1) is formed by radical cleavage of a disulfide bond existing in the main chain of the polyarylene sulfide resin derived from a raw material (sulfur element) at a melting temperature. It is considered that the generated sulfur radicals are bonded to 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 these structural units having a specific structure is characteristic of the polyarylene sulfide 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. 2-Iodobenzophenone is mentioned as a compound represented by General formula (2).

As the polymerization inhibitor having a carboxyl group, for example, one or more compounds selected from the compounds represented by the following general formula (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 the 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 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 represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ represents a monovalent group represented by general formula (a), (b) or (c).

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, and a hydrogen atom is preferable from the viewpoint of good reactivity. Examples of alkali metal atoms include sodium, lithium, potassium, rubidium, and cesium, with sodium being preferred. In 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, 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 the terminal structural unit having these specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the 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。）

(In the formula, R ⁵ represents a monovalent group represented by 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。）

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

As the polymerization inhibitor, a compound having no functional group such as a carboxyl group may be used. Examples of such a compound include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolyl sulfenamide, 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 a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and optionally by performing melt polymerization in a melt mixture obtained by heating a mixture containing a catalyst. To generate. The proportion of the diiodo aromatic compound in the molten mixture is preferably 0.5 to 2 mol, and more preferably 0.8 to 1.2 mol, based on 1 mol of elemental sulfur. The proportion of the polymerization inhibitor in the mixture is preferably 0.0001 to 0.1 mol, and more preferably 0.0005 to 0.05 mol, based on 1 mol of solid sulfur. ..

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

Nitro compounds can be added as catalysts to the molten mixture to control the rate of polymerization. Various nitrobenzene derivatives can be usually used as the nitro compound. Examples of the nitrobenzene derivative include 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 is usually an amount added as a catalyst, and for example, it is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur.

The conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds properly. The temperature of the melt polymerization is preferably 175° C. or higher and the melting point of the polyarylene sulfide resin to be produced+100° C. or lower, more preferably 180 to 350° C. The melt polymerization is carried out at an absolute pressure of preferably 1 [cPa] to 100 [kPa], more preferably 13 [cPa] to 60 [kPa]. The conditions for melt polymerization do not have to be constant. For example, at the initial stage of polymerization, the temperature is preferably in the range of 175 to 270° C., more preferably 180 to 250° C., and the absolute pressure is in the range of 6.7 to 100 [kPa], and then continuously or Polymerization is performed while stepwise heating and depressurizing, 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 generated +100° C. or less, 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]. In the present specification, 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 the oxidative crosslinking reaction, the melt polymerization is preferably performed 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.

The melt polymerization can be performed using, for example, 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 melt 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 with respect to a total of 100 parts by mass of the diiodo aromatic compound, elemental sulfur, the polymerization inhibitor, and the catalyst, if necessary. The content is in the range of 1 part by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. The amount of the solvent may be 0 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more.

After the molten mixture after the melt polymerization (reaction product) is cooled to obtain a solid-state mixture, the mixture is heated under reduced pressure or at atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. Good. As a result, not only the molecular weight can be further increased, but also the produced iodine molecules are sublimated and removed, so that the iodine atom concentration in the polyarylene sulfide resin can be suppressed to be 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 state mixture can be obtained. The heating after cooling to the solid state can be performed under the same temperature and pressure conditions as in melt polymerization.

The reaction product containing the polyarylene sulfide resin obtained by the melt polymerization step can be directly used as it is to produce a resin composition by a method such as charging into a melt kneader. It is preferable to prepare a dissolved product by adding a solvent in which the reaction product is dissolved and to take out the reaction product from the reaction apparatus in the state of the dissolved product because not only excellent productivity but also good reactivity are obtained. The addition of the solvent in which the reaction product dissolves is preferably carried out after the melt polymerization, but it may also be carried out in the latter stage of the reaction of the melt polymerization, and as described above, the molten mixture (reaction product) is cooled to a solid state. After the mixture is obtained, the mixture may be 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 of the heating dissolution may be in the range of the melting point of the solvent in which the reaction product is dissolved or higher, preferably in the range of 200 to 350°C, more preferably in the range of 210 to 250°C, and under pressure. It is preferable to carry out.

The mixing ratio of the solvent in which the reaction product is dissolved, which is used for preparing 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 Phillips method can be used. Examples of preferable solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone acid, and ε-caprolactam. , N-methyl-ε-caprolactam and other aliphatic cyclic amide compounds, hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF) and dimethylacetamide (DMA), and other amide compounds, polyethylene Examples include etherified polyethylene glycol compounds such as glycol dialkyl ethers (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). To be 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-pyrrolidion, 9- Fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4 -Dibenzoylputane, 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'-isopropylidene-diphenol, epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenylisophthalate, diphenyl-terphthalate and One or more solvents selected from the group consisting of 1-chloronaphthalene can be mentioned.

It is preferable that the melted product taken out from the reaction apparatus is subjected to post-treatment and then melt-kneaded with the other components to prepare a resin composition, because the reactivity becomes better. The method of post-treatment of the lysate is not particularly limited, but examples thereof include the following methods.
(1) The solvent is distilled off under reduced pressure or at normal pressure after the solution is added as it is or after adding an acid or a base, and then the solid matter after the solvent is distilled off is water, the solvent used for the solution. (Or an organic solvent having an equivalent solubility to a low molecular weight polymer), a solvent selected from acetone, methyl ethyl ketone, alcohols and the like once or twice or more, and further neutralized, washed with water, filtered and dried.
(2) Solvents such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons (soluble in the solvent of the dissolved matter and at least polyarylene) A solvent which is a poor solvent for the sulfide resin) is added as a precipitating agent to precipitate the solid product containing the polyarylene sulfide resin and the inorganic salt, and the solid product is separated by filtration, washed and dried. Method.
(3) The solvent used for the solution (or an organic solvent having an equivalent solubility to the low molecular weight polymer) is added to the solution, and the mixture is stirred and then filtered 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 and the like, followed by neutralization, washing with water, filtration and drying.

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

The reaction in which the polyarylene sulfide resin is formed by melt polymerization is illustrated 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) are, for example, polyphenylene when diphenyldisulfide having a substituent R containing a group represented by the general formula (a), (b) or (c) is used as a polymerization inhibitor. This is an example of a reaction that produces sulfide. The reaction formula (1) is a reaction in which the -S-S- bond in the polymerization inhibitor undergoes radical cleavage at the melting temperature. In the reaction formula (2), the sulfur radical generated in the reaction formula (1) attacks a carbon atom adjacent to the terminal iodine atom of the growing main chain, and the iodine atom is eliminated, so that the polymerization is stopped and This is a reaction in which the substituent R is introduced at the end of the main chain. The reaction formula (3) is a reaction in which the disulfide bond existing in the main chain of the polyarylene sulfide resin derived from the raw material (elemental sulfur) undergoes radical cleavage at the melting temperature. In the reaction formula (4), the polymerization is terminated by the recombination of the sulfur radical generated in the reaction formula (3) and the sulfur radical generated in the reaction formula (1), and the substituent R is attached to the end of the main chain. It is the reaction that is introduced. The released iodine atom is in a free state (iodine radical), or the iodine radicals are recombined as in the reaction formula (5) to generate an iodine molecule.

The reaction product containing the polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from the raw materials. Therefore, the polyarylene sulfide resin is usually used in the state of a mixture containing an iodine atom for preparation of a resin composition for spinning. The concentration of iodine atoms 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 polyarylene sulfide resin. It is also possible to suppress the iodine atom concentration to a low level by utilizing the sublimability of iodine molecules, and in that case, it is possible to set it to a range of 900 ppm or less, preferably 100 ppm or less, and further 10 ppm or less. Is. Furthermore, although it is possible to remove iodine atoms below the detection limit, it is not practical in view of productivity. The detection limit is, for example, about 0.01 ppm. The polyarylene sulfide resin of the present embodiment or a reaction product containing the same obtained by melt polymerization is a point containing an iodine atom, for example, a solution weight of a dichloroaromatic compound such as Phillips method in an organic polar solvent. It can be clearly distinguished from the polyarylene sulfide obtained by law.

As understood from the above reaction formula, the polyarylene sulfide resin obtained by melt polymerization is 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. It contains a main chain and a predetermined substituent R bonded to the end of the main chain. The predetermined substituent R is bonded to the aromatic ring at the terminal of the main chain directly or through a partial structure derived from the polymerization inhibitor.

The polyphenylene sulfide resin as the 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 represented by (arylene sulfide unit). The repeating unit represented by the formula (10) has 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。

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

The 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。

(In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.). , A repeating unit having a substituent as a side chain bonded to an aromatic ring. However, it is preferable that the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11) from the viewpoint of lowering the crystallinity and heat resistance. More specifically, the ratio of the repeating unit represented by the formula (11) is preferably the ratio of the repeating unit represented by the formula (10) and the repeating unit represented by the formula (11). It is 2% by mass or less, and more preferably 0.2% by mass or less.

The polyarylene sulfide resin of the present embodiment is mainly composed of the above-mentioned arylene sulfide unit, but is usually derived from the 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。

A structural unit relating to a disulfide bond represented by is also included in the main chain. From the viewpoint of heat resistance and mechanical strength, the ratio of the constituent unit represented by the formula (20) is preferably 2. with respect to the total of the arylene sulfide unit and the constituent site represented by the formula (20). The range is 9 mass% or less, and more preferably 1.2 mass% or less. It is preferable that the polyarylene sulfide resin contains the constitutional unit represented by the formula (20) in that the adhesion between the polyarylene sulfide resin composition and the metal is improved.

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

The weight average molecular weight of the polyarylene sulfide resin according to this embodiment is not particularly limited as long as the effects of the present invention are not impaired, but the lower limit thereof is 28,000 or more from the viewpoint of excellent mechanical strength. Is more preferable, and the range of 30,000 or more is more preferable. On the other hand, the upper limit is preferably in the range of 100,000 or less, more preferably 60,000 or less, and further 55,000 or less from the viewpoint that a better cavity balance can be imparted. Is most preferably in the range. Furthermore, from the viewpoint of being able to impart good cavity balance while being excellent in 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 and 100,000 or less may be used together with the polyarylene sulfide resin.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, more preferably 1.0 to 1.70. By setting the non-Newtonian index in such a range, the processability of the polyarylene sulfide resin can be improved and a good cavity balance can be imparted. In the present specification, the non-Newtonian index is an index that satisfies the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300°C. The non-Newtonian index can be an index relating to the molecular weight of the measurement target or the molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 1, it indicates that the molecular structure of the resin is linear. The larger the value, the more branching and cross-linking structure is contained.
D=α×S ⁿ
(In the above formula, D represents a shear rate, S represents a shear stress, α represents a constant, and n represents a non-Newtonian index.)

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

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

The polyarylene sulfide resin composition according to the present embodiment can contain one kind or two or more kinds of inorganic fillers. By blending the inorganic filler, a composition having high rigidity and high heat resistance stability can be obtained. Examples of the inorganic filler include powder fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate fillers such as talc and mica, glass beads, granular fillers such as silica beads and glass balloons, glass fibers. , Fibrous fillers such as carbon fibers and wollastonite fibers, and glass flakes. The polyarylene sulfide resin composition particularly preferably 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 5 to 200 parts by mass, and still more preferably 15 to 150 parts, relative to 100 parts by mass of the polyarylene sulfide resin. The range is parts by mass. When the content of the inorganic filler is within these ranges, a more excellent effect can be obtained in terms of maintaining the mechanical strength of the molded product.

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

Examples of the thermoplastic resin blended in the polyarylene sulfide resin composition include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, and polyethylene. , Polypropylene, polytetrafluoride ethylene, polydifluoride ethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester, etc.).

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) a polymer obtained by ring-opening polymerization of a lactam. Are listed. The polyamides can 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 a straight chain or a side chain and having 3 to 18 carbon atoms is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine. 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 may be used alone or in combination of two or more.

As the aromatic diamine, a diamine having a phenylene group and having 6 to 27 carbon atoms is preferable. Examples of suitable aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4,4'-. Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-di(m-aminophenoxy) Diphenyl sulfone, 4,4′-di(p-aminophenoxy)diphenyl sulfone, 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 may be used alone or in combination of two or more.

As the alicyclic diamine, a diamine having a cyclohexylene group and having 4 to 15 carbon atoms is preferable. Examples of suitable alicyclic diamine include 4,4′-diamino-dicyclohexylene methane, 4,4′-diamino-dicyclohexylene propane, 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 the dicarboxylic acid for obtaining the polyamide include an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an alicyclic dicarboxylic acid.

The aliphatic dicarboxylic acid is preferably a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms. Examples of 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, pracillic acid, tetradecane. Diacids, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid are included. 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 suitable aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid. Acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. .. These may be used alone or in combination of two or more. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can also be used within a range capable of being melt-molded.

As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferable. Examples of suitable aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These 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-enanthlactam, and η-capryllactam. These may be used alone or in combination of two or more.

Preferred combinations of polyamide raw materials include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine/adipic acid (nylon 6,6), 1,4-tetramethylenediamine/adipic acid (nylon 4,6). 1,6-hexamethylenediamine/terephthalic acid, 1,6-hexamethylenediamine/terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, 1,9-nonamethylenediamine/terephthalic acid Acid, 1,9-nonamethylenediamine/terephthalic acid/ε-caprolactam, 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid, and m-xylylenediamine/adipic acid. To be 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 The amide resin obtained is more preferable.

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 further preferably 5 to 45 parts with respect to 100 parts by mass of the polyarylene sulfide resin. The range is parts by mass. When the content of the thermoplastic resin other than the polyarylene sulfide resin is 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 blended in the polyarylene sulfide resin composition. Examples of thermoplastic elastomers include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In this specification, the thermoplastic elastomer is classified as an elastomer rather than the thermoplastic resin.

The elastomer (particularly the thermoplastic elastomer) preferably has a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group. This makes it possible to obtain a resin composition that is particularly excellent in terms of adhesiveness and impact resistance and that can suppress the amount of gas generated by heating. Examples of the 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 formula: R(CO)O(CO)- or R(CO)O- (in the formula, R represents an alkyl group having 1 to 8 carbon atoms). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an α-olefin with the 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 a functional group include, for example, α,β-unsaturated carboxylic acids such as (meth)acrylic acid and (meth)acrylic acid ester and their alkyl esters, maleic acid, fumaric acid, itaconic acid and Other examples include α,β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their derivatives (mono- or diesters, their acid anhydrides, etc.), and glycidyl (meth)acrylate. Among these, an epoxy group, a carboxyl group, and a formula: R(CO)O(CO)- or R(CO)O- (in the formula, R represents an alkyl group having 1 to 8 carbon atoms). An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the groups shown are preferable from the viewpoint of improving the toughness and impact resistance.

The content of the elastomer cannot be unconditionally specified because it varies depending on its type and use, but for example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. To 100 parts by mass, more preferably 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 heat resistance and toughness of the molded product.

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

The epoxy resin is preferably an aromatic epoxy resin. 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 novolac type epoxy resin, cresol novolac. 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 resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-contracted novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, and biphenyl novolac type epoxy resin. These aromatic epoxy resins can be used alone or in combination of two or more kinds. Among these aromatic epoxy resins, novolac type epoxy resins are preferable, and cresol novolac type epoxy resins are more preferable, from the viewpoint of excellent compatibility with other resin components.

The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably 3 to 100 parts by mass, and further preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. The range is 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 product can be remarkably obtained.

The polyarylene sulfide resin composition may contain a silane compound having a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group. This makes it possible to obtain a resin composition that improves the compatibility of the polyarylene sulfide resin with other components and that suppresses the amount of gas generated by heating. Examples of the silane compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyl. Examples include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

The content of the silane compound is, for example, preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass 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 can be obtained.

The polyarylene sulfide resin composition according to the present embodiment may contain other additives such as a release agent, a colorant, a heat resistance stabilizer, a UV stabilizer, a foaming agent, a rust preventive, a flame retardant and a lubricant. Good. The content of the additive is preferably 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 pelletized compound by a method of melt-kneading the polyarylene sulfide resin obtained by the above method and the above-mentioned other components. The temperature of the melt-kneading is preferably in the range of 250 to 350°C, and more preferably in the range of 290 to 330°C. Melt-kneading can be performed using a twin-screw extruder or the like.

Polyarylene sulfide resin composition according to the present embodiment, alone or in combination with the materials such as the other components, injection molding, extrusion molding, compression molding and various melt processing methods such as blow molding, heat resistance, It can be processed into a molded product having excellent moldability and dimensional stability. 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 products.

The molded product thus obtained is suitably used for surface mount electronic parts. The surface mount electronic component has, for example, a molded product of a polyarylene sulfide resin composition and a metal terminal as components, and is fixed on a printed or printed wiring board or circuit board by a surface mounting method. is there. In order to fix this electronic component to the substrate by the surface mounting method, the metal terminal of the electronic component is placed on the surface of the substrate so as to be in contact with the current-carrying portion on the substrate through the solder ball, and the reflow furnace is heated by the above heating method. There is a method of soldering the electronic component to the substrate by heating at. Specific examples of such surface mount electronic components include connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, and IC and LED housings for surface mount systems. ..

When the polyarylene sulfide resin composition according to the present embodiment is used for a surface mount 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 polyarylene sulfide resin composition according to the present embodiment exhibits excellent mechanical strength even when molded into a molded product having a snap fit portion, for example.

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 characteristics]
・Compliance test method...ASTM D-790
-Test piece... 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (long)
・Test results...Average number of tests n=10

[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 (long)
・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 result: Average value of test number n=5

[Metal adhesion strength]
A 4 x 10 x 49 mm metal piece (SUS304) set in a mold was injected with a polyarylene sulfide resin composition of the same dimensions and molded, and a tensile test was conducted under conditions of a chuck distance of 20 mm and a pulling speed of 1 mm/min. Was carried out and the metal adhesion strength was measured.

[Cavity balance]
Using a washer mold having 40 cavities, the PPS compound was injection-molded under the minimum molding conditions as long as the cavity closest to the primary sprue (C1) 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 pressure holding.

After molding, the filling degree of the cavity (C10) farthest from the primary sprue in the same runner as the cavity (C1) was compared. The filling degree (mass %) was determined from the mass ratio of the molded product of the cavity (C1) 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 filling degree, the cavity balance of each composition was judged according to the following criteria.
AA: 100 to 90% by mass range A: 89 to 80% by mass range B: 79 to 70% by mass range C: 69 to 60% by mass range D: 59% by mass or less range

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

[Reflow heating resistance]
The resin composition pellets were molded using an injection molding machine to prepare 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, this box-shaped connector was placed on a printed 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-stage criteria.
◯: No change in appearance.
X: Blister or melting was observed.
(Reflow condition)
The reflow heating was performed with an infrared reflow device (“TPF-2” manufactured by Asahi Engineering Co., Ltd.). As heating conditions at this time, after preheating at 180° C. for 100 seconds, heating and holding were performed until the surface of the substrate reached 280° C. That is, the temperature profile (temperature curve) is reflowed so that the temperature is 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. The settings were made by, and heating and holding were performed.

2. Synthesis of Polyphenylene Sulfide Resin (PPS Resin) (Synthesis Example 1: Synthesis of PPS-1)
300.0 g of p-diiodobenzene (Tokyo Kasei Co., Ltd., p-diiodobenzene purity 98.0% or more), solid sulfur (Kanto Chemical Co., Inc., sulfur (powder)) 27.00 g, 4,4′- 2.0 g of dithiobisbenzoic acid (Wako Pure Chemical Industries, Ltd., 4,4′-dithiobisbenzoic acid, Technical Grade) was heated to 180° C., and they were dissolved and mixed under nitrogen. Next, the temperature was raised to 220° C., and the pressure was reduced to an absolute pressure of 26.6 kPa. The resulting melted mixture was melt-polymerized for 8 hours by gradually changing the temperature and pressure so that the absolute pressure became 133 Pa at 320°C. After the reaction was completed, 200 g of NMP was added, the mixture was heated and stirred at 220° C., and the obtained dissolved substance was filtered. 320 g of NMP was added to the lysate after filtration, and cake washing filtration was performed. 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 ion-exchanged water at 70° C. was added to the filtered cake to wash the cake. Ion-exchanged water (1 L) was added to the obtained water-containing cake and stirred for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged 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 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". It was

(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 in place 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 water-NMP mixture was distilled off by raising the temperature to 200° C. under a nitrogen atmosphere. Next, to this system, a solution of 292.53 g (1.99 mol) of p-dichlorobenzene and 1.62 g (0.01 mol) of 2,5-dichloroaniline dissolved in 230 g of NMP was added, and the mixture was heated at 220° C. for 5 hours. Further, the reaction was carried out at 240° C. for 2 hours under a nitrogen atmosphere. The contents were taken out after cooling from the reaction vessel, a part thereof 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 under reduced pressure at 80° C. to obtain powdery amino group-containing polyphenylene sulfide (PPS-4).

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

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 a 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 with terephthalic acid ("Genestar N1000A" manufactured by Kuraray Co., Ltd.)
PA46: Polyamide 46 (manufactured by DS Japan Engineering Plastics Co., Ltd., "Stanyl TS300")
(Inorganic filler)
GF: Glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

[Production and evaluation of compound]
Each raw material was uniformly mixed by a tumbler with the composition shown in Table 1, and then melt-kneaded at 300° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine) to obtain a pelletized compound. The obtained compound was injection-molded under the conditions of a cylinder temperature of 300° C. and a mold temperature of 140° C. to prepare a test piece used for a bending property, a metal adhesion strength, a cavity balance and a hot water resistance test, and various evaluations were performed. .. In addition, the amount of gas generated was measured for the PPS resin simple substance and the compound. The evaluation results are shown in Table 2.

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 (bending strength, bending elongation at break), metal adhesion strength, cavity balance, hot water resistance, gas It was superior to PPS-4 in terms of the amount generated.

Claims (22)

Polyarylene sulfide resin,
At least one other resin component selected from the group consisting of 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, which comprises:
The polyarylene sulfide resin is 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. That you can get,
1 to 300 parts by mass of the other resin component with respect to 100 parts by mass of the polyarylene sulfide resin,
The surface-mounted electronic component is a molded product obtained by molding a polyarylene sulfide resin composition, and a metal terminal ,
The polyarylene sulfide resin composition for surface-mounted electronic components is characterized by further containing an inorganic filler,
Polyarylene sulfide resin composition for surface-mounted electronic parts.
(However, with 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-mounted electronic components, which comprises:
The polyarylene sulfide resin is 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. That you can get,
The polyarylene sulfide resin has at least one group selected from the group consisting of carboxyl groups derived from the polymerization inhibitor and salts of carboxyl groups,
Except for 100 parts by mass of the polyarylene sulfide resin, the polyarylene sulfide resin composition in which the other component is 1 to 300 parts by mass is excluded. ) The polyarylene sulfide resin composition for surface-mounted electronic components according to claim 1, wherein the polyarylene sulfide resin has at least one group selected from the group consisting of a hydroxy group derived from the polymerization inhibitor and an amino group. .. The polyarylene sulfide resin,
The following general formula (20) is contained in the main chain.

The surface-mounted electron according to claim 1, which is a mixture of a polyarylene sulfide resin having a disulfide bond represented by: and a mixture containing an iodine atom in a ratio of 0.01 to 10,000 ppm based on the polyarylene sulfide resin. Polyarylene sulfide resin composition for parts. The following general formula (20) is contained in the main chain.

The polyarylene sulfide resin having a disulfide bond represented by
The following general formula (1-1) at the end

(In the formula, Y is a hydroxy group or an amino group.), or a monovalent group represented by the following general formula (2-1).

The polyarylene sulfide resin composition for surface-mounted electronic components according to claim 3, which has a monovalent group represented by: The polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70,
The polyarylene sulfide resin composition for surface-mounted electronic components according to claim 1, wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. 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-mounted electronic components according to claim 1, wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. Claim 1 is obtained by molding the polyarylene sulfide resin composition according to any one of 6, a surface mount electronic component molded article. A molded article for surface mount electronic parts obtained by molding the polyarylene sulfide resin composition, and a metal terminal, a surface mount electronic component,
The polyarylene sulfide resin composition,
Polyarylene sulfide resin,
At least one other resin component selected from the group consisting of a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups;
Containing
The polyarylene sulfide resin, by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a melt mixture containing the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor. That you can get,
1 to 300 parts by mass of the other resin component relative to 100 parts by mass of the polyarylene sulfide resin,
Surface mount electronic parts characterized by .
(However, with 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, which comprises:
The polyarylene sulfide resin, by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a melt mixture containing the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor. That you can get,
The polyarylene sulfide resin has at least one group selected from the group consisting of salts of carboxyl groups and carboxyl groups derived from the polymerization inhibitor,
Excluding 100 parts by mass of the polyarylene sulfide resin, a polyarylene sulfide resin composition in which the other component is 1 to 300 parts by mass. ) The surface-mounted electronic component according to claim 8, wherein the polyarylene sulfide resin composition for surface-mounted electronic component further contains an inorganic filler. The surface mount electronic component according to claim 8, wherein the polyarylene sulfide resin has at least one group selected from the group consisting of a hydroxy group derived from the polymerization inhibitor and an amino group. The polyarylene sulfide resin,
The following general formula (20) is contained in the main chain.

9. The surface-mounted electron according to claim 8, which is a mixture of a polyarylene sulfide resin having a disulfide bond represented by: and a mixture containing an iodine atom in a ratio of 0.01 to 10,000 ppm based on the polyarylene sulfide resin. parts. The following general formula (20) is contained in the main chain.

The polyarylene sulfide resin having a disulfide bond represented by
The following general formula (1-1) at the end

(In the formula, Y is a hydroxy group or an amino group.), or a monovalent group represented by the following general formula (2-1).

The surface mount electronic component according to claim 11, which has a monovalent group represented by: The polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70,
The surface mount electronic component according to claim 8, wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. 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 surface mount electronic component according to claim 8, wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. Polyarylene sulfide resin,
Surface mounting by melt-kneading with a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and at least one other resin component selected from the group consisting of crosslinkable resins having two or more crosslinkable functional groups A method for producing a polyarylene sulfide resin composition for electronic parts,
The polyarylene sulfide resin, by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a melt mixture containing the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor. To get,
The surface-mounted electronic component, comprising a molded product obtained by molding a polyarylene sulfide resin composition, and a metal terminal,
A method for producing a polyarylene sulfide resin composition for surface-mounted electronic parts, comprising:
(However, with polyarylene sulfide resin,
Melt kneading with 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 crosslinkable resins having two or more crosslinkable functional groups. thing,
The polyarylene sulfide resin, by a method comprising reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a melt 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 salts of carboxyl groups and carboxyl groups derived from the polymerization inhibitor,
And a method for producing a polyarylene sulfide resin composition for surface-mounted electronic components. ) The polyarylene sulfide resin composition for surface mount electronic components further contains an inorganic filler,
Polyarylene sulfide resin,
An inorganic filler,
Melt-kneading a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and at least one other component selected from the group consisting of crosslinkable resins having two or more crosslinkable functional groups,
A method for producing the polyarylene sulfide resin composition for surface-mounted electronic components according to claim 15 . The polyarylene sulfide resin composition for surface-mounted electronic components according to claim 15 , wherein the polyarylene sulfide resin has at least one group selected from the group consisting of a hydroxy group derived from the polymerization inhibitor and an amino group. Manufacturing method. The polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70,
The method for producing a polyarylene sulfide resin composition for surface-mounted electronic components according to claim 15 , wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. 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 method for producing a polyarylene sulfide resin composition for surface-mounted electronic components according to claim 15 , wherein the Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. The polymerization inhibitor has the following general formula (1) or the following general formula (2):

The method for producing a polyarylene sulfide resin composition for surface-mounted electronic components according to claim 15 , which is a compound represented by the formula (Y is a hydroxy group or an amino group). To produce the claims 15 to surface mount electronic component polyarylene sulfide resin composition by the method according to any one of 20, the produced polyarylene sulfide resin composition, injection molding, extrusion molding, A method for producing a molded article for surface-mounted electronic component, which comprises processing by a 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 product and a metal terminal,
Soldering a surface-mounted electronic component, which includes a molded product and a metal terminal, to a substrate by heating in a reflow oven,
A method for manufacturing a surface mount electronic component, wherein the molded product is manufactured by the manufacturing method according to claim 21 .