JP2021113319A - Polyarylene sulfide resin composition, molded article thereof, and surface mounting electronic component - Google Patents

Abstract

To provide a polyarylene sulfide resin composition capable of suppressing gas generation amount by heating, and excellent properties in a resin composition or a molded article thereof, a molded article using the resin composition, and an electronic component having the molded article.SOLUTION: There is provided a polyarylene sulfide resin composition for surface mounting electronic component containing a polyarylene sulfide resin, and at least one kind of other component selected from a group consisting of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide, an elastomer, and 2 or more crosslinkable functional group, in which the polyarylene sulfide resin is one capable of being obtained by a method including a reaction of a diiode aromatic compound, an elemental sulfur, and a polymerization inhibitor in a melting mixture containing the diiode aromatic compound, the elemental sulfur, and the polymerization inhibitor.SELECTED DRAWING: None

Description

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 electrical and electronic industries, the mounting method of resin-based electronic components on a printed circuit board may be abbreviated as the surface mount method (hereinafter, "SMT method") with the miniaturization of products and the improvement of productivity. ) Is shifting to a 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 this SMT method, but in recent years, due to the problem of environmental pollution, tin has been used as an alternative material. Lead-free solder with several types of metals added to the base is used.

Such lead-free solder has a higher melting point than tin-lead eutectic solder. For example, in the case of tin-silver eutectic solder, the melting point reaches 220 ° C. 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, there is a strong demand for a resin material having high heat resistance as a resin material used for surface mount electronic components.

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

International Publication No. 2009/096401

However, in the conventional composition containing a polyarylene sulfide resin, the amount of gas generated by heating during molding is relatively large, and there is a risk of corroding the metal terminals of electronic parts. Further, in the conventional polyarylene sulfide resin composition or a molded product thereof, 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 that the amount of gas generated by heating can be suppressed while preventing the surface mount electronic components from melting or deforming in the heating furnace (reflow furnace), and the resin composition or 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 provided with the molded product are provided. To provide.

As a result of various studies, 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 terminal, and have completed the present invention.

That is, the present invention is 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, at least one. A polyarylene sulfide resin composition for a surface-mounted electronic component containing other components of a species, wherein the polyarylene sulfide resin contains a diiode aromatic compound, a simple sulfur, and a polymerization inhibitor. The present invention relates to a polyarylene sulfide resin composition for a surface-mounted electronic component, which can be obtained by a method including reaction in a molten mixture containing a group compound, a simple sulfur and a polymerization inhibitor.

According to the present invention, it is possible to prevent the surface mount electronic components from melting or deforming in the heating furnace (reflow furnace) and to suppress the amount of gas generated by heating, and the resin composition or its molded product is excellent. An object of the present invention is to provide a polyarylene sulfide resin composition having mechanical strength, metal adhesion, and cavity balance characteristics, a molded product using the resin composition, and a surface mount electronic component including the molded product.

The cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded products are molded at the same time by injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is not sufficient, molding defects such that some cavities are not sufficiently filled tend to occur.

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

In the polyarylene sulfide resin used in the present embodiment, the diiode aromatic compound, elemental sulfur, and a polymerization inhibitor are reacted in a molten mixture containing the diiode aromatic compound, elemental sulfur, and the polymerization inhibitor. It can be obtained by the method including. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with a conventional method such as the Philips method.

A diiodot aromatic compound has an aromatic ring and two iodine atoms directly attached to the aromatic ring. Examples of the diiodine 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 preferable that the substitution positions are 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 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 aryl sulfone and an aryl ketone. It may be substituted with at least one substituent selected from. However, from the viewpoint of 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. More specifically, the present invention may be used elemental sulfur which is commercially available as Tsuboneho medicament may be obtained generically, may be used a mixture containing S ₈ and S ₆ and the like. The purity of elemental sulfur is also not particularly limited. Elemental sulfur may be in the form of grains or powder as long as it is solid at room temperature (23 ° C.). The particle size of the 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 prohibits 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 hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group at the end of the main chain of the polyarylene sulfide resin. That is, as the polymerization inhibitor, a compound having at least one or two or more groups selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group is preferable. Further, the polymerization inhibitor may have the above-mentioned functional group, or the above-mentioned functional group may be generated by a polymerization termination reaction or the like.

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

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

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。

In the group represented by the formula (1-1) or (2-1), a disulfide bond derived from a raw material (elemental sulfur) in the main chain of a polyarylene sulfide resin is radically cleaved at a melting temperature. It is considered that the generated sulfur radical is introduced into the polyarylene sulfide resin by binding to the compound represented by the general formula (1) or the compound represented by the general formula (2). The presence of the structural units of these specific structures 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. Examples of the compound represented by the general formula (2) include 2-iodobenzophenone.

As the polymerization inhibitor having a carboxyl group, for example, one or more compounds selected from the 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 the general formula (3), R ¹ and R ² independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and R ¹ or R 2 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 the general formula (5), R ⁴ represents a monovalent group represented by the 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, but a hydrogen atom is preferable from the viewpoint of good reactivity. Examples of the alkali metal atom include sodium, lithium, potassium, rubidium, cesium and the like, but sodium is preferable. In the general formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In the general formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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), the monovalent group represented by the following formula (6) or (7) is introduced as the terminal group of the main chain. The presence of the terminal structural units of these specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compounds represented by the general formulas (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 the 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。）

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

As the polymerization inhibitor, a compound or the like that does not have a functional group such as a carboxyl group may be used. Examples of such compounds 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 subjected to melt polymerization in a melt mixture obtained by heating a mixture containing a diiode aromatic compound, elemental sulfur, a polymerization inhibitor and, if necessary, a catalyst. Generate. The ratio of the diiodo aromatic compound in the melt mixture is preferably in the range of 0.5 to 2 mol, more preferably in the range of 0.8 to 1.2 mol, with respect to 1 mol of elemental sulfur. 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, based on 1 mol of solid sulfur. ..

The timing of adding the polymerization inhibitor is not particularly limited, but the mixture containing the diiode aromatic compound, elemental sulfur and a catalyst added as needed is heated, and the temperature of the mixture is preferably 200 ° C. to 320 ° C. The polymerization inhibitor can be added when the temperature reaches the range, more preferably 250 to 320 ° C.

The polymerization rate can be adjusted by adding a nitro compound as a catalyst to the melt mixture. As this nitro compound, various nitrobenzene derivatives can be usually used. Examples of the nitrobenzene derivative include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diiodo-4-nitroamine. The amount of the catalyst may be an amount usually added as a catalyst, and is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur, for example.

The conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably 175 ° C. or higher, the melting point of the produced polyarylene sulfide resin + 100 ° C. or lower, and more preferably 180 to 350 ° C. The melt polymerization is carried out with an absolute pressure preferably in the range of 1 [cPa] to 100 [kPa], more preferably in the range of 13 [cPa] to 60 [kPa]. The conditions for melt polymerization do not have to be constant. For example, in the initial stage of polymerization, the temperature is preferably in the range of 175 to 270 ° C., more preferably in the range of 180 to 250 ° C., and the absolute pressure is in the range of 6.7 to 100 [kPa], and then continuously or continuously. Polymerization is carried out stepwise while raising the temperature and reducing the pressure, and in the latter stage of the polymerization, the temperature is preferably set to 270 ° C. or higher, the melting point of the polyarylene sulfide resin to be produced + 100 ° C. or lower, and 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 the resin means a value measured according to JIS K 7121 using a differential scanning calorimeter (PerkinElmer DSC device Pyris Diamond).

Melt polymerization is preferably carried out in a non-oxidizing atmosphere from the viewpoint of obtaining a high degree of polymerization while preventing an oxidative cross-linking reaction. In a non-oxidizing atmosphere, the oxygen concentration of the gas phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, and even more preferably the gas phase contains substantially no oxygen. The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium and argon.

The melt polymerization can be carried out by using, for example, a melt kneader equipped with a heating device, a depressurizing 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 preferably contains substantially no solvent. More specifically, the amount of the solvent contained in the melt mixture is preferably 10 parts by mass with respect to 100 parts by mass in total of the diiode aromatic compound, elemental sulfur, the polymerization inhibitor and, if necessary, the catalyst. The range is less than a part, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. The amount of the solvent may be in the range of 0 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more.

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

The reaction product containing the polyarylene sulfide resin obtained in the melt polymerization step can be directly put into a melt kneader or the like to produce a resin composition, but the reaction product is said to be the same. It is preferable to prepare a lysate by adding a solvent in which the reaction product dissolves, and to take out the reaction product from the reaction apparatus in the state of the lysate because not only the productivity is excellent but also the reactivity is further improved. The addition of the solvent in which the reaction product dissolves is preferably carried out after the melt polymerization, but it may be carried out in the latter stage of the reaction of the melt polymerization, and the melt mixture (reaction product) is cooled as described above to be in a solid state. After obtaining the mixture of, the mixture may be heated under pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere to further proceed the polymerization reaction. The step of preparing the lysate may be carried out in a non-oxidizing atmosphere. The temperature for heating and dissolving may be in the range above the melting point of the solvent in which the reaction product dissolves, 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 with.

The blending ratio of the solvent in which the reaction product dissolves used for preparing the solution 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 preferable compounds are N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone acid, ε-caprolactam. , N-Methyl-ε-caprolactam and other aliphatic cyclic amide compounds, hexamethylphosphate triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA) and other amide compounds, polyethylene. Examples thereof include 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 are 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, pentachlorophenyl, 1-benzyl-2-pyrrolidion, 9- Fluolenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4 -Dibenzoylptan, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o, o'-biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thiantorene, 3-phenoxybenzyl alcohol, 4- Phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4,4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluorantene, diphenylphthalate, diphenylcarbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxy Naphthalene, 4-bromodiphenyl ether, pyrene, 9,9'-bifluorene, 4,4'-isopropyllidene-diphenol, epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenylisophthalate, diphenyl-terphthalate and Included is one or more solvents selected from the group consisting of 1-chloronaphthalene.

It is preferable that the dissolved 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 for post-treatment of the dissolved substance is not particularly limited, and examples thereof include the following methods.
(1) The solvent is distilled off from the solution as it is or after adding an acid or a base, and then the solvent is distilled off under reduced pressure or at normal pressure, and then the solid after distilling off the solvent is water, the solvent used for the solution. (Or an organic solvent having the same solubility as a low molecular weight polymer), a method of washing once or twice or more with a solvent selected from acetone, methyl ethyl ketone, alcohols and the like, and further neutralizing, washing with water, filtering and drying.
(2) Solvents such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons in the solution (soluble in the solvent of the solution and at least polyarylene). A solvent that is a poor solvent for the sulfide resin) is added as a precipitant to precipitate the solid product containing the polyarylene sulfide resin and the inorganic salt, and the solid product is filtered, washed and dried. Method.
(3) The solvent used for the lysate (or an organic solvent having the same solubility as that of the low molecular weight polymer) is added to the lysate, 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, and then neutralizing, washing with water, filtering and drying.

In the post-treatment methods as illustrated in (1) to (3) above, the polyarylene sulfide resin may be dried in a vacuum, in the air, or in an atmosphere of an inert gas such as nitrogen. You may. 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 produced by the polyarylene sulfide resin 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。

The reaction formulas (1) to (5) are polyphenylene when, for example, diphenyldisulfide having a substituent R containing a group represented by the general formulas (a), (b) or (c) is used as a polymerization inhibitor. This is an example of a reaction in which sulfide is produced. The reaction formula (1) is a reaction in which the —S—S— bond in the polymerization inhibitor radically cleaves at a melting temperature. In the reaction formula (2), the sulfur radical generated in the reaction formula (1) attacks the adjacent carbon atom of the terminal iodine atom of the growing main chain, and the iodine atom is eliminated, so that the polymerization is stopped and the polymerization is stopped. This is a reaction in which a substituent R is introduced at the end of the main chain. The reaction formula (3) is a reaction in which a disulfide bond existing from a raw material (single sulfur) in the main chain of a polyarylene sulfide resin is radically cleaved at a melting temperature. In the reaction formula (4), the polymerization is stopped 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 at the end of the main chain. It is a reaction to be introduced. The desorbed iodine atom is in a free state (iodine radical), or the iodine radicals recombine with each other as shown 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 material. Therefore, the polyarylene sulfide resin is usually used in the state of a mixture containing iodine atoms for the preparation of a resin composition for spinning and the like. The concentration of iodine atoms in the mixture is, for example, in the range of 0.01 to 10000 ppm, preferably in the range of 10 to 5000 ppm with respect to the polyarylene sulfide resin. It is also possible to keep the iodine atom concentration low by utilizing the sublimation property of the iodine molecule, and in that case, it is also possible to set it in the 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 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 polyarylene sulfide resin contains an iodine atom, and thus contains a solution weight of a dichloroaromatic compound such as the Phillips method in an organic polar solvent. It can be clearly distinguished from legally obtained polyarylene sulfides.

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

The polyphenylene sulfide resin as the polyarylene sulfide resin according to the embodiment is described by, 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 (allylene sulfide unit) represented by. The repeating unit represented by the formula (10) is connected at the para position in the following formula (10a):

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）：

The following formula (10b) that combines with the repeating unit represented by and 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.

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 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 include repeating units having substituents as side chains attached to the aromatic ring. However, from the viewpoint of lowering the crystallinity and heat resistance, it is preferable that the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11). More specifically, the ratio of the repeating unit represented by the formula (11) is preferably the sum 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, more preferably 0.2% by mass or less.

The polyarylene sulfide resin of the present embodiment is mainly composed of the above allylene sulfide units, but is usually derived from the elemental sulfur of the raw material, according to 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 structural unit related to the 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. The range is 9% by mass or less, more preferably 1.2% by mass or less. It is preferable that the polyarylene sulfide resin contains the structural 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, and more preferably in the range of 0.99 to 1.30. By setting Mw / Mtop 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, Mw indicates the weight average molecular weight measured by gel permeation chromatography, and Mtop indicates the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram obtained by the measurement is maximized. Mw / Mtop indicates the distribution of the molecular weight to be measured. Normally, when this value is close to 1, the distribution of the molecular weight is narrow, and as this value is large, the distribution of the molecular weight is wide. The measurement conditions for gel permeation chromatography are the same as those used in the examples herein. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw / Mtop.

The weight average molecular weight of the polyarylene sulfide resin according to the present embodiment is not particularly limited as long as the 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 preferable, and more preferably in the range of 30,000 or more. On the other hand, the upper limit is preferably in the range of 100,000 or less, more preferably in the range of 60,000 or less, and further in the range of 55,000 or less from the viewpoint that a better cavity balance can be imparted. It is most preferably in the range of. Further, from the viewpoint of excellent mechanical strength and being able to impart a good cavity balance, 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-Nutonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, more preferably in the range of 1.0 to 1.70. By setting the non-neutonian 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 refers to an index that satisfies the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300 ° C. The non-Nutonian index can be an index related to the molecular weight to be measured or the molecular structure such as linear, branched, or crosslinked. Normally, when this value is close to 1, it indicates that the molecular structure of the resin is linear. The larger the value, the more branched and crosslinked structures are included.
D = α × ^Sn
(In the above equation, D represents the shear rate, S represents the shear stress, α represents a constant, and n represents the non-Nutonian exponent.)

The polyarylene sulfide resin having the above-mentioned specific range of Mw / Mtop and non-neutonian index includes, for example, a diiode aromatic compound, a simple substance sulfur, a polymerization inhibitor, a diiode aromatic compound, a simple substance sulfur and a polymerization inhibitor. In the method of reacting (solution polymerization) in a molten mixture containing the above, it can be obtained by increasing the amount of the polyarylene sulfide resin to some extent.

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

The polyarylene sulfide resin composition according to the present embodiment may 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, 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 preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.

The content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and further preferably in the range of 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 in these ranges, a better 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 can 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, polysulphon, polyethersulfone, polyetheretherketone, polyetherketone, and polyethylene. , Polypropylene, polytetrafluorinated ethylene, polydifluorinated 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 diamine and dicarboxylic acid, (ii) a polymer obtained by polycondensation of aminocarboxylic acid, and (iii) a polymer obtained by ring-opening polymerization of lactam. Can be mentioned. The polyamide can be used alone or in combination of two or more.

Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As the aliphatic diamine, a diamine having a linear or side chain and having 3 to 18 carbon atoms is preferable. Examples of suitable aliphatic diamines are 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-undecamethylenediamine, 1,12-dodecamethylene Diamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexamethylenediamine, 1,17-heptadecamethylenediamine, 1,18 − Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. These can 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'-diaminodiphenylsulphon, 4,4'-diaminodiphenylsulphon, 4,4'-diaminodiphenylsulfide, 4,4'-di (m-aminophenoxy) Diphenyl sulphon, 4,4'-di (p-aminophenoxy) diphenyl sulphon, 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 Included are 2,2'-dimethylbenzidine.
These can 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 diamines are 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl-. Included are dicyclohexylene methane, 1,4-diaminocyclohexane, and piperazine. These can be used alone or in combination of two or more.

Examples of the dicarboxylic acid for obtaining a polyamide include an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an alicyclic dicarboxylic acid.

As the aliphatic dicarboxylic acid, a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable. Examples of suitable aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, placeric acid, tetradecane. Examples include diacid, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can 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 are isophthalic acid, terephthalic acid, methylterephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid. Examples thereof include acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulphon-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. .. These can be used alone or in combination of two or more. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range that can be melt-molded.

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

Examples of the lactam for obtaining a polyamide include ε-caprolactam, ω-laurolactam, ζ-enantractam, and η-caprilactam. These can 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 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 The rearmid resin to be 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 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 thermoplastic resin other than the polyarylene sulfide resin is in these ranges, the effect of further improving the heat resistance, chemical resistance and mechanical properties can be obtained.

As the elastomer to be blended in the polyarylene sulfide resin composition, a thermoplastic elastomer is often used. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In addition, in this specification, a thermoplastic elastomer is classified into an elastomer instead of 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 the carboxyl group. As a result, it is possible to obtain a resin composition that is particularly excellent in terms of adhesiveness, impact resistance, etc., 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 the α-olefin 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 α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like. Other examples include α, β-unsaturated dicarboxylic acid having 4 to 10 carbon atoms and a derivative thereof (mono or diester, an acid anhydride 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- (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 represented groups are preferable from the viewpoint of improving toughness and impact resistance.

The content of the elastomer cannot be unconditionally specified because it differs depending on the type and application, but for example, it is preferably in the range of 1 to 300 parts by mass, and more preferably 3 with respect to 100 parts by mass of the polyarylene sulfide resin. It is in the range of ~ 100 parts by mass, more preferably 5 to 45 parts by mass. When the content of the elastomer is within these ranges, an even 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 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.

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 novolac type epoxy resin, and cresol novolac. Type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl Examples thereof include type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak 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. Among these aromatic epoxy resins, a novolac type epoxy resin is preferable, and a cresol novolac type epoxy resin is more preferable, because it is excellent in compatibility with other resin components.

The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 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. It is in the range of parts by mass. When the content of the crosslinkable resin is in these ranges, the effect of improving the rigidity and heat resistance of the molded product is particularly remarkable.

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 a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group. As a result, it is possible to obtain a resin composition capable of improving the compatibility between the polyarylene sulfide resin and other components and suppressing the amount of gas generated by heating. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples thereof 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 in 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 mold release agent, a colorant, a heat stabilizer, an ultraviolet 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, for example.

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

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

The molded product thus obtained is suitably used for surface mount electronic components. The surface mount electronic component is, for example, a molded product of a polyarylene sulfide resin composition and a metal terminal as components, and is fixed on a printed wiring board or circuit board by a surface mount method. be. In order to fix the electronic component to the substrate by the surface mount method, the metal terminal of the electronic component is placed on the substrate surface so as to be in contact with the energized portion on the substrate via a solder ball, and the inside of the reflow furnace is subjected to the above heating method. A method of soldering the electronic component to the substrate by heating with the above can be mentioned. Specific examples of such surface mount electronic components include connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, IC and LED housings, etc. for surface mount methods. ..

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, according to the polyarylene sulfide resin composition according to the present embodiment, excellent mechanical strength is exhibited even when molded into, for example, a molded product having a snap-fit portion.

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

1. 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 (length)
・ Test result: Average value of the number of tests n = 10

[Heat-resistant water]
The test piece was immersed in hot water at 95 ° C., and the change in bending strength with 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 items: Retention rate of flexural strength after 1000 hours and 3000 hours with respect to initial strength-Test results: Average value of the number of tests n = 5

[Metal adhesion strength]
A tensile test was performed on a 4 × 10 × 49 mm metal piece (SUS304) set in a mold by injecting and molding a polyarylene sulfide resin composition having the same dimensions under the conditions of a chuck distance of 20 mm and a tensile speed of 1 mm / min. 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 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 (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 determined according to the following criteria.
AA: Range of 100 to 90% by mass A: Range of 89 to 80% by mass B: Range of 79 to 70% by mass C: Range of 69 to 60% by mass D: Range of 59% by mass or less

[Gas generation amount]
Using a gas chromatograph mass spectrometer, a predetermined amount of 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]
The pellets of the resin composition 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 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.
〇: No change in appearance.
X: Blister or melting was observed.
(Reflow condition)
The reflow heating was performed by an infrared reflow device (“TPF-2” manufactured by Asahi Engineering Co., Ltd.). As the heating conditions at this time, after preheating each at 180 ° C. for 100 seconds, heating and holding was 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 in the region of 200 ° C. or higher, 90 seconds in the region of 220 ° C. or higher, 80 seconds in the region of 240 ° C. or higher, and 60 seconds in the region of 260 ° C. or higher. The setting was made in, and heating was held.

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 of 98.0% or more), 27.00 g of solid sulfur (manufactured by Kanto Chemical Co., Inc., sulfur (powder)), 4,4'- 2.0 g of dithiobis benzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobis benzoic acid, Technical Grade) was heated to 180 ° C. to dissolve and mix them 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 melt mixture was melt-polymerized for 8 hours by gradually changing the temperature and pressure so as to have an absolute pressure of 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 obtained lysate was filtered. 320 g of NMP was added to the lysate after filtration, and cake washing and filtration were 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. 1 L of ion-exchanged water was added to the obtained hydrous cake, and the mixture was 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'-dithiobis benzoic acid". rice field.

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

(Synthesis Example 4: Synthesis of PPS-4)
600 g of N-methylpyrrolidone and 336.3 g (2.0 mol) of sodium sulfide pentahydrate were charged in a 2 L autoclave, and the temperature was raised to 200 ° C. in a nitrogen atmosphere to distill off the water-NMP mixture. Next, 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 this system, and the mixture was added at 220 ° C. for 5 hours. The reaction was further carried out at 240 ° C. for 2 hours in a nitrogen atmosphere. After cooling, the contents were taken out from the reaction vessel, a part 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 a powdered 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. 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% of terephthalic acid, 25 mol% of isophthalic acid, and 10 mol% of adipic acid as essential monomer components (melting point 310 ° C., Tg 120 ° C.).
PA9T: Polyamide obtained by reacting nonanediamine with terephthalic acid (manufactured by Kuraray Co., Ltd., "Genesta N1000A")
PA46: Polyamide 46 (manufactured by DSM Japan Engineering Plastics Co., Ltd., "Stanil TS300")
(Inorganic filler)
GF: Glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

[Preparation and evaluation of compound]
Each raw material was uniformly mixed by a tumbler with the compounding composition shown in Table 1, and then melt-kneaded at 300 ° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine Co., Ltd.) to obtain a pellet-shaped compound. The obtained compound was injection-molded under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 140 ° C. to prepare test pieces used for bending characteristics, metal adhesion strength, cavity balance and heat resistance and water resistance test, and various evaluations were performed. .. In addition, the amount of gas generated was measured for the PPS resin alone 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 (flexural strength, bending elongation), metal adhesion strength, cavity balance, heat resistance and water gas. It was superior to PPS-4 in terms of the amount of generation.

Claims (6)

Polyarylene sulfide resin and
With 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
By a method in which the polyarylene sulfide resin comprises reacting a diiode aromatic compound, elemental sulfur, and a polymerization inhibitor in a melt mixture containing the diiode aromatic compound, the elemental sulfur, and the polymerization inhibitor. A polyaromatic sulfide resin composition for surface-mounted electronic parts, which can be obtained. The surface-mounted electronic component according to claim 1, wherein the polyarylene sulfide resin has 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 derived from the polymerization inhibitor. Polyarylene sulfide resin composition for. The polyarylene sulfide resin has a Mw / Mtop of 0.80 to 1.70.
The polyarylene sulfide resin composition for surface mount electronic components according to claim 1 or 2, wherein Mw and Mtop are weight average molecular weights and peak molecular weights measured by gel permeation chromatography, respectively. The polyarylene sulfide resin has a non-Nutonian 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 components according to any one of claims 1 to 3, wherein Mw and Mtop are weight average molecular weights and peak molecular weights measured by gel permeation chromatography, respectively. A molded product for surface mount electronic components obtained by molding the polyarylene sulfide resin composition according to any one of claims 1 to 4. A surface mount electronic component comprising the molded product according to claim 5 and a metal terminal.