JP2009263635A - Thermoplastic resin composition, process for producing the same, and electronic component for surface mounting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant resin composition which can hold a chlorine atom content within a thermoplastic resin composition to ≤900 ppm, which is an unprecedentedly low level, and has both heat-resistance and flame retardancy, and to provide its production process and an electronic component for surface mounting. <P>SOLUTION: The resin composition comprises a polyarylene sulfide resin (A) and polyamide (B) as essential components, wherein the content of the polyamide (B) based on 100 pts.mass of the composition is 10-30 pts.mass, and the extraction rate is less than 7 mass% when the composition is extracted with hexafluoro isopropanol at 70°C for 15 minutes. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition containing a polyarylene sulfide resin and polyamide, a method for producing the same, and an electronic component for surface mounting.

  Polyarylene sulfide resins typified by polyphenylene sulfide resins have a high melting point, excellent flame resistance and chemical resistance, and good fluidity during molding. Widely used in parts, machine parts and automobile parts.

  In recent years, in the field of electrical and electronic industries, with the miniaturization of products and the improvement of productivity, the mounting method of resin-based electronic components on a printed circuit board is a so-called surface mount method (hereinafter abbreviated as “SMT method”). It has shifted to the surface mounting method called. Conventionally, a tin-lead eutectic solder (melting point: 184 ° C.) is generally used as a technology for mounting electronic components on a substrate by this SMT method. However, in recent years, tin has been used as an alternative material due to environmental pollution problems. So-called lead-free solder in which several kinds of metals are 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. There is a problem that when the resin-based electronic component such as the connector is soldered, the electronic component is melted or deformed in the heating furnace (reflow furnace). Therefore, a resin material having high heat resistance has been strongly demanded as a resin material for surface mount electronic components.

  Then, the resin composition obtained by melt-kneading polyarylene sulfide resin and aromatic polyamide is known as a highly heat-resistant resin material (for example, refer patent document 1 and patent document 2). However, polyarylene sulfide resins and aromatic polyamides are generally poorly compatible and it is difficult to uniformly mix them, so the low hygroscopicity, which is a weak point of the aromatic polyamides, appears significantly. There has been a problem that blisters are likely to occur in the appearance of the electronic component that has passed through the furnace (reflow furnace). Furthermore, since the dispersibility of the aromatic polyamide in the composition is low, flammability, which is also a weak point of the aromatic polyamide, tends to be exhibited, resulting in a decrease in flame retardancy of the molded product.

Furthermore, in recent years, in the field of electrical and electronic industries, switching to halogen-free materials has been proceeding at a rapid pace from the viewpoint of reducing the environmental load. For example, JPCA (ES-1-1999), IEC (61249-2-21), The guidelines for electrical and electronic parts such as IPC (4101B) strongly demand that the content of chlorine atoms in a trace analysis be 900 ppm or less. However, since the polyarylene sulfide resin uses paradichlorobenzene as a raw material, a chloro group remains at the terminal, making it difficult to use it as a halogen-free material. In this regard, the material in which the polyarylene sulfide and the aromatic polyamide are blended is an effective means for reducing the chlorine atom content in the material because the polyarylene sulfide is diluted by the blending of the aromatic polyamide. .
However, since the polyarylene sulfide resin itself usually contains about several thousand ppm of chlorine atoms, even if the polyamide is blended and diluted, the above-mentioned criteria of chlorine atom content in the material of 900 ppm or less can be cleared. It was difficult. In order to improve this, there is a method in which the polyarylene sulfide resin is washed to reduce the amount of chlorine atoms, but in this case, not only the amount of chlorine atoms but also the amount of functional groups having reactivity with the polyamide component is simultaneously reduced. As a result, the compatibility between the polyarylene sulfide resin and the polyamide component is reduced, and the flame retardancy is reduced as described above.

JP-A-2-123159 JP-A-5-5060

  Accordingly, the problem to be solved by the present invention is that the chlorine atom content in the thermoplastic resin composition can be controlled to an unprecedented low level of 900 ppm or less, and has both heat resistance and flame resistance. It is in providing a conductive resin composition, its manufacturing method, and an electronic component for surface mounting.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the extraction rate when extracted with hexafluoroisopropanol at 70 ° C. for 15 minutes in a thermoplastic resin composition containing a polyarylene sulfide resin and a polyamide component is 7 mass. %, The inventors have found that the chlorine atom content in the composition can be reduced and that excellent reflow heat resistance and flame retardancy can be imparted to the molded product, and the present invention has been completed.

  That is, the present invention is a resin composition comprising a polyarylene sulfide resin (A) and a polyamide (B) as essential components, and the content of the polyamide (B) per 100 parts by mass of the composition is 10 It relates to a thermoplastic resin composition characterized in that it is -30 parts by mass and the extraction rate when the composition is extracted with hexafluoroisopropanol at 70 ° C for 15 minutes is 7% by mass or less.

  In the present invention, the polyarylene sulfide resin (A) and the polyamide (B) are further biaxially kneaded and extruded at a ratio of 10 to 30 parts by mass of the polyamide (B) per 100 parts by mass of the total mass of the blended components. The condition that the ratio (discharge amount / screw rotation number) of the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is 0.02 to 0.2 (kg / hr · rpm). The present invention relates to a method for producing a thermoplastic resin composition, characterized in that the temperature of the resin melted and kneaded below and discharged is in the range of 345 to 370 ° C.

  The present invention further relates to a surface-mounting electronic component characterized in that a molded product of the thermoplastic resin composition and a metal terminal are essential components.

  According to the present invention, a thermoplastic resin composition that can control the chlorine atom content in the thermoplastic resin composition to an unprecedented low level of 900 ppm or less, and has excellent heat resistance and flame retardancy. , Its manufacturing method, and electronic components for surface mounting can be provided.

  Therefore, the thermoplastic resin composition of the present invention is particularly useful for connectors, switches, relays, coil bobbins, capacitors, etc. used for soldering onto a printed circuit board in the SMT method.

FIG. 1 is a graph showing a temperature profile in an infrared heating furnace in a blister resistance test.

  The polyarylene sulfide resin (A) used in the present invention is not particularly limited, but has a peak in the molecular weight range of 25,000 to 40,000 in measurement using gel permeation chromatography, and non- Those having a Newton index in the range of 0.9 to 1.3 are preferred. Thus, the polyarylene sulfide resin (A) having a so-called linear structure having a relatively high molecular weight and a non-Newtonian index in the range of 0.9 to 1.3 has a lower chlorine atom weight in the resin. It becomes. Further, the polyarylene sulfide resin (A) has a reactivity with the polyamide (B) such that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 5-10. It is preferable from the viewpoint that performances excellent in heat resistance and mechanical strength of the molded product can be exhibited. The polyarylene sulfide resin (A) has a peak in a molecular weight range of 25,000 to 40,000 in gel permeation chromatography measurement, and Mw / Mn is from the point that the features of the present invention become more remarkable. Particularly preferred are those in the range of 6.5 to 8.5 and the non-Newtonian index in the range of 1.0 to 1.2.

  The polyarylene sulfide resin (A) preferably has a chlorine atom content of 1,500 to 2,000 ppm from the viewpoint of reducing the amount of chlorine atoms in the thermoplastic resin composition.

  Further, the polyarylene sulfide resin (A) preferably has a Na content of 1000 ppm or less, particularly 500 ppm or less. Thus, by reducing the Na content in the polyarylene sulfide resin (A), the reactivity with other compounding components such as polyamide (B) and a coupling agent is improved, contributing to a decrease in the extraction rate. The flame retardancy will be even better.

The polyarylene sulfide resin (A) has a melt viscosity η (A) in the range of 25 to 100 Pa · s at 350 ° C. and a shear rate of 100 sec ^{−1 with} the polyamide (B). It is preferable from the viewpoint of compatibility.

  The polyarylene sulfide resin (A) (hereinafter abbreviated as “PAS resin (A)”) has a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Is the following structural formula (1)

（式中、Ｒ^５及びＲ^６は、それぞれ独立的に水素原子、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、エトキシ基を表す。）
で表される構造部位を繰り返し単位とする樹脂である。

(In the formula, R ⁵ and R ⁶ 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.)
It is resin which makes the structural site represented by a repeating unit.

Here, in the structural part represented by the structural formula (1), R ⁵ and R ⁶ in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin (A), In that case, what couple | bonds in the para position represented by following Structural formula (2) and what couple | bonds in the meta position represented by following Structural formula (3) are mentioned.

  Among these, the heat resistance and crystallinity of the PAS resin (A) include that the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2). It is preferable in terms of

  In addition, the PAS resin (A) includes not only the structural portion represented by the structural formula (1) but also the following structural formulas (4) to (7).

で表される構造部位を、前記構造式（１）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本発明では上記構造式（４）〜（７）で表される構造部位は１０モル％以下であることが、ＰＡＳ樹脂（Ａ）の耐熱性、機械的強度の点から好ましい。
前記ＰＡＳ樹脂（Ａ）中に、上記構造式（４）〜（７）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。

The structural site represented by the formula (1) may be included in an amount of 30 mol% or less of the total with the structural site represented by the structural formula (1). In particular, in the present invention, the structural site represented by the structural formulas (4) to (7) is preferably 10 mol% or less from the viewpoint of the heat resistance and mechanical strength of the PAS resin (A).
In the case where the PAS resin (A) includes a structural portion represented by the structural formulas (4) to (7), the bonding mode thereof is either a random copolymer or a block copolymer. Also good.

  The PAS resin (A) has the following structural formula (8) in its molecular structure.

で表される３官能性の構造部位、或いは、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、１モル％以下であること、特に実質的には含まれないことがＰＡＳ樹脂（Ａ）中の塩素原子含有量低減の観点から好ましい。

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, etc., but it is 1 mol% or less, particularly substantially, relative to the total number of moles with other structural sites. It is preferable that it is not contained in the viewpoint of reducing the chlorine atom content in the PAS resin (A).

Such a PAS resin (A) can be produced by, for example, the following (1) to (4).
(1) A method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane,
(2) A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate,
(3) A method of polymerizing in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent,
(4) Method by self-condensation of p-chlorothiophenol

  Among these, the method of (1) reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is easy to control the reaction. From the viewpoint of excellent productivity.

  Among the methods (1), a linear and high molecular weight PAS resin (A) can be industrially efficiently produced. Among the methods (1), solid alkali metal sulfide, dichlorobenzene, alkali metal hydrosulfide, A method in which a reaction slurry containing an organic acid alkali metal salt as an essential component is prepared, and heated to perform polymerization in a heterogeneous system is particularly preferable. Specifically, such a polymerization method includes:

Step 1:
Hydrous alkali metal sulfide, or
Hydrous alkali metal hydrosulfide and alkali metal hydroxide;
N-methylpyrrolidone and
A non-hydrolyzable organic solvent,
A step of producing a slurry (I) by reacting while dehydrating,
Step 2:
Next, in the slurry (I),
Dichlorobenzene,
The alkali metal hydrosulfide;
A step of reacting the alkali metal salt of the hydrolyzate of N-methylpyrrolidone to perform polymerization,
Is preferable from the viewpoint of productivity.

  Examples of the hydrated alkali metal sulfide used here include liquid or solid hydrates of compounds such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, and the solid content concentration thereof is 10 to 80% by mass. In particular, it is preferably 35 to 65% by mass.

  Examples of the hydrous alkali metal hydrosulfide include liquid or solid hydrates of compounds such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. The partial concentration is preferably 10 to 80% by mass. Among these, hydrated lithium hydrosulfide and hydrated sodium hydrosulfide are preferable, and hydrated sodium hydrosulfide is particularly preferable.

  Furthermore, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and aqueous solutions thereof. In addition, when using this aqueous solution, it is preferable that it is an aqueous solution with a density | concentration of 20 mass% or more from the point that the spin-drying | dehydration process of the process 1 is easy. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable.

The PAS resin (A) can be measured for the molecular weight using gel permeation chromatography and the molecular weight distribution (Mw / Mn) under the following conditions.
[Measurement conditions by gel permeation chromatography]
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (SSC-7000 manufactured by Senshu Kagaku Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measuring method: The molecular weight distribution and the peak molecular weight are measured using 6 types of monodisperse polystyrene for calibration with a UV detector (360 nm). The molecular weight measured by this method preferably has a peak in the range of 25000 to 30000, more preferably 26000 to 29000. Further, from the viewpoint of compatibility with the aromatic polyamide (B), those having a melt viscosity by a flow tester in the range of 40 to 60 Pa · S, more preferably 45 to 55 Pa · S are preferable. In addition, a measurement is the value measured using the Koka type flow tester at 300 degreeC, shear rate 100sec < ^-1 >, nozzle hole diameter 0.5mm, and length 1.0mm.

  The PAS resin (A) described in detail above further reduces moisture content by reducing the amount of residual metal ions, and further reduces the residual amount of low molecular weight impurities by-produced during polymerization. It is preferable that after A) is produced, it is treated with an acid and then washed with water.

  The acid that can be used here is preferable in that acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid can efficiently reduce the amount of residual metal ions without decomposition of the PAS resin (A). Acetic acid and hydrochloric acid are preferred.

  Examples of the acid treatment method include a method of immersing the PAS resin in an acid or an aqueous acid solution. At this time, further stirring or heating may be performed as necessary.

  Here, as a specific method of the acid treatment, for example, in the case of using acetic acid, first, an aqueous acetic acid solution having a pH of 4 is heated to 80 to 90 ° C., and the PAS resin (A) is immersed in the solution. The method of stirring for 40 minutes is mentioned. In this invention, Na content in the above-mentioned PAS resin (A) can be reduced by performing sufficient acid treatment in this way.

  The acid-treated PAS resin (A) is then washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.

  Further, the PAS resin (A) to be subjected to the acid treatment is preferably a powder, specifically, a granular material such as a pellet or a polymer in a slurry state after polymerization. Good.

  Next, the polyamide (B) used in the present invention is not particularly limited, but the one having a melting point of 280 to 330 ° C. has good compatibility with the PAS resin (A) and is molded. It is preferable from the point that the heat resistance of the product is also good. In particular, the melting point of the polyamide (B) is preferably 290 to 330 ° C., particularly preferably 310 to 330 ° C., from the viewpoint that these effects become remarkable.

  Specifically, the polyamide (B) is polyamide 26 which is a polymer of adipic acid and ethylenediamine, polyamide 46 which is a polymer of adipic acid and tetramethylenediamine, nylon 6 which is an ε-caprolactam polymer, Aliphatic polyamides such as nylon 11 which is an undecane lactam polymer, nylon 12 which is a lauryl lactam polymer, nylon 66 which is a hexamethylenediamine / adipic acid cocondensate, and nylon 610 which is a hexamethylenediamine / sebacic acid cocondensate Or an aromatic polyamide, but the PAS resin (A) is an aliphatic polyamide having 2 to 4 carbon atoms in the aliphatic hydrocarbon moiety such as polyamide 46 and polyamide 26, or an aromatic polyamide. Good compatibility with the heat resistance of the molded product Point becomes good, from the viewpoint of heat resistance after reflow is improved in electronic component applications, particularly for surface mounting.

  Specifically, the aromatic polyamide used here has the following structural formula a.

で表されるテレフタル酸アミド構造を繰り返し構造単位の一つとして有するものである。
前記構造式ａ中、Ｒは炭素原子数２〜１２アルキレン基を表す。かかるテレフタル酸アミド構造は、具体的には、テレフタル酸、又はテレフタル酸ジハライドと、炭素原子数２〜１２の脂肪族ジアミンとの反応によって形成されるものである。ここで用いる炭素原子数２〜１２の脂肪族ジアミンは、具体的には、エチレンジアミン、プロパンジアミン、１，４−ブタンジアミン、１，６−ヘキサンジアミン、１，７−ヘプタンジアミン、１，８−オクタンジアミン、１，９−ノナンジアミン、１，１０−デカンジアミン、１，１１−ウンデカンジアミン、１，１２−ドデカンジアミン等の直鎖状脂肪族アルキレンジアミン；１−ブチル−１，２−エタンジアミン、１，１−ジメチル−１，４−ブタンジアミン、１−エチル−１，４−ブタンジアミン、１，２−ジメチル−１，４−ブタンジアミン、１，３−ジメチル−１，４−ブタンジアミン、１，４−ジメチル−１，４−ブタンジアミン、２，３−ジメチル−１，４−ブタンジアミン、２−メチル−１，５−ペンタンジアミン、３−メチル−１，５−ペンタンジアミン、２，５−ジメチル−１，６−ヘキサンジアミン、２，４−ジメチル−１，６−ヘキサンジアミン、３，３−ジメチル−１，６−ヘキサンジアミン、２，２−ジメチル−１，６−ヘキサンジアミン、２，２，４−トリメチル−１，６−ヘキサンジアミン、２，４，４−トリメチル−１，６−ヘキサンジアミン、２，４−ジエチル−１，６−ヘキサンジアミン、２，２−ジメチル−１，７−ヘプタンジアミン、２，３−ジメチル−１，７−ヘプタンジアミン、２，４−ジメチル−１，７−ヘプタンジアミン、２，５−ジメチル−１，７−ヘプタンジアミン、２−メチル−１，８−オクタンジアミン、３−メチル−１，８−オクタンジアミン、４−メチル−１，８−オクタンジアミン、１，３−ジメチル−１，８−オクタンジアミン、１，４−ジメチル−１，８−オクタンジアミン、２，４−ジメチル−１，８−オクタンジアミン、３，４−ジメチル−１，８−オクタンジアミン、４，５−ジメチル−１，８−オクタンジアミン、２，２−ジメチル−１，８−オクタンジアミン、３，３−ジメチル−１，８−オクタンジアミン、４，４−ジメチル−１，８−オクタンジアミン、５−メチル−１，９−ノナンジアミン等の分岐鎖状脂肪族アルキレンジアミン；シクロヘキサンジアミン、メチルシクロヘキサンジアミン、イソホロンジアミン、ノルボルナンジメチルアミン、トリシクロデカンジメチルアミン等の脂環族ジアミン類が挙げられる。

As a repeating structural unit.
In the structural formula a, R represents an alkylene group having 2 to 12 carbon atoms. Specifically, the terephthalic acid amide structure is formed by a reaction between terephthalic acid or terephthalic acid dihalide and an aliphatic diamine having 2 to 12 carbon atoms. Specific examples of the aliphatic diamine having 2 to 12 carbon atoms used herein include ethylenediamine, propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and 1,8- Linear aliphatic alkylenediamine such as octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3- Til-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2, 2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6 -Hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1 , 7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1, -Octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1 , 8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl-1 Branched aliphatic alkylene diamines such as 1,9-nonanediamine; and alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethylamine.

  Among these, a linear aliphatic alkylene diamine having 4 to 8 carbon atoms and a branched aliphatic alkylene diamine having 5 to 10 carbon atoms are particularly preferable from the viewpoint of moisture resistance and mechanical strength.

  The aromatic polyamide has the following structural formula b in addition to the terephthalic acid amide structure.

（式中、Ｒは構造式ａのおけるＲと同義である。）
で表されるイソフタル酸アミド構造を有することが、前記芳香族ポリアミド自体の融点を下げてＰＡＳ樹脂（Ａ）との相溶性を改善できる点から好ましい。

(Wherein R has the same meaning as R in structural formula a)
Is preferable from the viewpoint that the melting point of the aromatic polyamide itself can be lowered to improve the compatibility with the PAS resin (A).

  Further, the aromatic polyamide has the following structural formula c in addition to the terephthalic acid amide structure.

（式中、Ｒは構造式ａのおけるＲと同義であり、Ｒ^２は、炭素原子数４〜１０の脂肪族炭化水素基を表す。）で表される酸アミド構造を有していてもよい。

(Wherein R has the same meaning as R in structural formula a, and R ² represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms). Good.

  Here, the acid amide structure represented by the structural formula c includes an aliphatic dicarboxylic acid having 4 to 10 carbon atoms, an acid esterified product thereof, an acid anhydride thereof, or an acid halide thereof and 2 to 12 carbon atoms. It is formed by reaction with an aliphatic diamine. Specifically, the aliphatic dicarboxylic acid having 4 to 10 carbon atoms used here is malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, Aliphatic dicarboxylic acids such as 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; fats such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Aliphatic dicarboxylic acids such as cyclic dicarboxylic acids.

  Specific examples of the acid esterified product of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms include methyl ester, ethyl ester, t-butyl ester, and the like. Examples of the halogen atom constituting the acid halide include a bromine atom and a chlorine atom.

As described above, the aromatic polyamide preferably has an amide structure represented by the structural formula a, structural formula b, or structural formula c as a structural site, and is composed of one dicarboxylic acid molecule and one diamine molecule. When the acid amide structure is 1 unit, the terephthalic acid amide structure is 65 mol% or more and the isophthalic acid amide structure is 20 mol% or more with respect to the total acid amide structure constituting the aromatic polyamide (B). It is preferable that the aliphatic hydrocarbon acid amide structure is contained in an amount of 10 mol% or more from the viewpoint that the effect of improving the heat resistance becomes remarkable.
Furthermore, the aromatic polyamide has a terephthalic acid amide structure represented by the structural formula a of 65 to 70 mol% from the balance between heat resistance and moisture resistance.
20-25 mol% of isophthalic acid amide structure represented by the structural formula b,
5-15 mol% of an acid amide structure represented by the structural formula c,
Polyamide composed of

The polyamide (B) used in the present invention has a melt viscosity η of 350 ° C. and a shear rate of 100 sec ⁻¹ at 25 to 100 Pa · s from the viewpoint of dispersibility in the PAS resin (A). Preferably, the value of η _B / η _A is 0.9 to 5.0 when the melt viscosity of the polyamide is η _B and the melt viscosity of the PAS resin (A) is η _A. In particular, the range of 0.9 to 3.0 is preferable from the viewpoint of compatibility between the polyamide and the PAS resin (A). The polyamide preferably has a Tg of 90 to 140 ° C. from the viewpoint of heat resistance.

The polyamide (B) can be produced, for example, by the following methods (1) to (3).
(1) After dissolving an acid halide of a dicarboxylic acid component and a diamine component containing an aliphatic diamine having 2 to 12 carbon atoms in two kinds of solvents that are not compatible with each other, an alkali and a catalytic amount of quaternary An interfacial polymerization method in which two liquids are mixed and stirred in the presence of an ammonium salt to carry out a polycondensation reaction.
(2) A solution in which an acid halide of a dicarboxylic acid component and a diamine component containing an aliphatic diamine having 2 to 12 carbon atoms are reacted in an organic solvent in the presence of an alkaline compound that accepts an acid such as a tertiary amine. Polymerization method.
(3) A melt polymerization method in which an amide exchange reaction is performed in a molten state using a diesterified product of a dicarboxylic acid component and an aromatic diamine as raw materials.

  As described above, the blending ratio of the PAS resin (A) and the polyamide (B) in the thermoplastic resin composition of the present invention includes 100 parts by mass of the thermoplastic resin composition of the present invention, that is, other blending components described later. The amount of the polyamide (B) is 100 to 30 parts by mass, preferably 12 to 22 parts by mass per 100 parts by mass of the total composition. By adjusting to such a range, the amount of chlorine atoms in the composition can be effectively reduced, and heat resistance and flame retardancy can be combined at a high level. In the present invention, the blending ratio of the PAS resin (A) and the polyamide (B) is in the range of 95/5 to 60/40 in terms of the mass ratio of the PAS resin (A) / polyamide (B). The range of / 20 to 60/40 is preferable from the viewpoint of excellent balance between heat resistance and flame retardancy.

  In the thermoplastic resin composition of the present invention, the content of the polyamide (B) per 100 parts by mass of the composition is 10 to 30 parts by mass, and the composition is hexafluoroisopropanol at 70 ° C. 15 It is characterized in that the extraction rate when extracted for a minute is 7% by mass or less. Here, the extraction rate when the composition is extracted with hexafluoroisopropanol at 70 ° C. for 15 minutes is a value obtained by dividing the mass of the component extracted with hexafluoroisopropanol by the total mass of the composition. It can be determined from the following measurement method. Polyamide is soluble in hexafluoroisopropanol, but the amount of polyamide extracted with hexafluoroisopropanol is lower than the polyamide content in the resin composition. This suggests that it is in a form that is difficult to dissolve, and that it is presumed that a good polymer alloy of PAS resin / polyamide is formed, and this is considered to improve heat resistance. In particular, the content of polyamide (B) in the polyarylene sulfide resin of the present invention is X (mass%), and the extraction rate when the composition is extracted with hexafluoroisopropanol at 70 ° C. for 15 minutes is Y (mass%). In this case, the value of Y / X is preferably in the range of 0.01 to 0.40.

(How to determine the extraction rate of hexafluoroisopropanol)
The pellet of the composition is freeze-ground using a freeze-pulverizer, passed through a sieve having an opening of 500 μm, and then about 1 g of the ground sample is precisely weighed into a 20-ml sample tube, and 4 ml of hexafluoroisopropanol (HFIP) is added. Add. Next, the sample tube containing the sample and HFIP is sonicated with an ultrasonic cleaner at 70 ° C. for 15 minutes. Furthermore, the sonication liquid was quantitatively transferred to a filter with a precisely weighed mass and filtered. Then, the filter is dried and weighed, and the mass of the filtration residue is measured. The difference between the mass weighed before the treatment and the mass after drying (excluding the mass of the filter) is the mass of the extracted component, and the value obtained by dividing this by the mass weighed before the treatment is expressed as a percentage. The extraction rate.

  In the present invention, by further using the reactive functional group-containing organosilane (C), the compatibility between the PAS resin (A) and the polyamide (B) is improved, and the effect of improving heat resistance and flame retardancy is more remarkable. It is preferable from the point which becomes a thing. Here, the compounding ratio of the reactive functional group-containing organosilane (C) is preferably contained at a ratio of 0.01 to 2 parts by mass per 100 parts by mass of the thermoplastic resin composition of the present invention.

  Specific examples of the reactive functional group in the reactive functional group-containing organosilane (C) include an epoxy group, an amino group, and an isocyanate group. The reactive functional group-containing organosilane (C) is specifically a silane compound having two or more alkoxy groups on the Si atom together with the various reactive functional groups described above. Here, examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms, or a polyalkyleneoxy group composed of 2 to 6 units using the alkoxy group as a repeating unit. Examples of such compounds include γ-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, and 3-isocyanatopropyltriethoxy. Silane, 2- (3,4 epoxy cyclohexyl) trimethoxysilane, etc. are mentioned.

  The thermoplastic resin composition of the present invention uses an epoxy resin such as a novolak cresol type epoxy resin or a phenol novolak type epoxy resin as a crosslinking agent together with or in place of the reactive functional group-containing organosilane (C). You can also.

  In addition, the thermoplastic resin composition of the present invention includes a PAS resin (A), an aromatic polyamide (B), and more preferably each component of the reactive functional group-containing organosilane (C), and further hydrotalcites. Combining the compound (D) suppresses thermal decomposition of the polymer component during the melt-kneading of the PAS resin (A) and the aromatic polyamide or during the heat treatment in the reflow furnace of the molded product, and has excellent mechanical strength. In view of further improving the flame retardancy and the effect of improving the appearance of the molded article after heat treatment, it is preferable.

The hydrotalcite compound (D) used here has a layered crystal structure of a divalent metal ion and a trivalent metal ion hydroxide, and has a structure including an anion between the layers of the layered crystal structure. It is an inorganic compound or a fired product thereof. Examples of the divalent metal ions constituting the hydrotalcite compound (D) include Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , and Zn ^2+. The ions include Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , and In ³⁺ . Further, the anions include OH ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , NO ₃ ⁻ , CO ₃ ⁻ , SO ₄ ²⁻ , Fe (CN) ₆ ³⁻ and CH ₃ COO ⁻ , molybdate, polymolybtenene. Acid ions, vanadate ions, and polyvanadate ions may be mentioned.

Among these, in particular, the trivalent metal ion is Al ³⁺ because it is excellent in ion exchange ability with the acid component derived from the polyarylene sulfide resin (A) and has a remarkable effect of preventing gas generation. The ion is preferably CO ₃ ⁻ , specifically, for example, the following formula M ²⁺ _1-x Al _x (OH) _2. (CO ₃ ) _{X / 2} mH ₂ O Formula 1
(In Formula 1, M ²⁺ represents a divalent metal ion selected from the group consisting of Mg, Ca and Zn, and x and m are numerical values satisfying 0 <x <0.5 and 0 ≦ m ≦ 2. .)
It is preferable that it is a compound represented by these.

The compound satisfying the formula 1 is, for example,
^{_{Mg 2+ 6 Al 2 (OH)}} 16 · (CO 3) · 4H 2 O
In addition to natural hydrotalcite represented by
Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15 · 0.54H ₂ O,
_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O,
_{Mg 4.3 Al 2 (OH) 12.6} CO 3 · 3.5H 2 O,
Mg _4.2 Al ₂ (OH) _12.4 CO ₃ ,
Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Examples thereof include Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O.
Among these, in the present invention, in order to prevent gas generation, the following formula 2
Mg ²⁺ _1-x Al _x (OH) _2. (CO ₃ ) _{X / 2} mH ₂ O Formula 2
(In Formula 2, x and m are numerical values satisfying 0 <x <0.5 and 0 ≦ m ≦ 2.)
It is particularly preferable that the Mg-Al hydrotalcite-like compound represented by

  The blending amount of the hydrotalcite compound (D) is 0.1 to 1.0% by mass in the thermoplastic resin composition of the present invention, or the PAS resin from the viewpoint that the effect of preventing gas generation is remarkable. It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of total mass of (A) and the said aromatic polyamide, and it is especially preferable that it is 0.1-2 mass parts.

  In the present invention, it is preferable from the viewpoint of the mechanical strength of the molded product that a fibrous reinforcing material (E-1) or an inorganic filler (E-2) is further blended in addition to the above components.

  Examples of the fibrous reinforcing material (E-1) include glass fibers, PAN-based or pitch-based carbon fibers, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, and boric acid. Examples thereof include aluminum fibers, potassium titanate fibers, inorganic fibrous materials such as stainless steel, aluminum, titanium, copper, brass and other metallic fibrous materials, and organic fibrous materials such as aramid fibers.

  The inorganic filler (E-2) includes, for example, silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbestos, alumina silicate, zeolite, pyrophyllite, calcium carbonate, magnesium carbonate, Carbonate such as dolomite, sulfate such as calcium sulfate and barium sulfate, metal oxide such as alumina, magnesium oxide, silica, zirconia, titania and iron oxide, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, etc. Is mentioned. These fibrous reinforcing materials (E-1) and inorganic fillers (E-2) may be used alone or in combination of two or more.

  The amount of the fibrous reinforcing material (E-1) or inorganic filler (E-2) used in the present invention is 1 with respect to 100 parts by mass of the total amount of the PAS resin (A) and the aromatic polyamide (B). It is preferable to be in the range of ~ 200 parts by weight. The fibrous reinforcing material (E-1) or the inorganic filler (E-2) is a surface treatment agent such as a silane coupling agent or a titanium coupling agent as long as the performance of the heat-resistant resin molded article of the present invention is not impaired. The surface treatment may be performed.

  Furthermore, in the thermoplastic resin composition of the present invention, an antioxidant or a stabilizer (F) may be used in combination with the PAS resin (A) and the aromatic polyamide as long as the effects of the present invention are not impaired. Suppressing the thermal decomposition of polymer components during melt-kneading or heat treatment in the reflow oven of the molded product, further improving the mechanical strength and flame retardancy, and improving the appearance of the molded product after heat treatment This is preferable because the effect becomes more remarkable. Antioxidants or stabilizers include, for example, phenolic (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, and quinoline antioxidants (or stabilizers). included.

  In order to maintain heat resistance stably for a long period of time, an antioxidant or a stabilizer may be included. Antioxidants or stabilizers include, for example, phenolic (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, and quinoline antioxidants (or stabilizers). included.

  Phenol antioxidants include hindered phenols such as 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol). 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) Hydroxyphenyl) propionate], n-octadecyl-3- (4 ′, 5′-di-t-butylphenol) propionate, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) ) Propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl- 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocin Namamide), 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane and the like are included.

Among the hindered phenols, e.g., 1,6-hexanediol - bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] _C 2 _{-C 10} alkylene diols, such as - bis [ 3- (3,5-di - branched _C 3 -C ₆ alkyl-4-hydroxyphenyl) propionate]; triethylene glycol - bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ] di- or Toriokishi _C 2 -C ₄ alkylene diol such as - bis [3- (3,5-di - branched _C 3 -C ₆ alkyl-4-hydroxyphenyl) propionate]; glycerin tris [3- (3,5 - di -t- butyl-4-hydroxyphenyl) propionate] _C 3, such as -C ₈ alkylene triol - bis [3- (3 5-di - branched _C 3 -C ₆ alkyl-4-hydroxyphenyl) propionate]; pentaerythritol tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] _C 4, such as -C ₈ alkylene tetrols tetrakis [3- (3,5-di - branched _C 3 -C ₆ alkyl-4-hydroxyphenyl) propionate] and the like are preferable.

Amine-based antioxidants include hindered amines such as tri- or tetra-C ₁ -C ₃ alkyl piperidines or derivatives thereof [eg 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, bis (tri-, tetra- or _penta-C 1 -C ₃ alkyl _piperidine) C 2 _{-C 20} Alkylene dicarboxylic acid esters [for example, bis (2,2,6,6-tetramethyl-4-piperidyl) ogisalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate], 1,2-bis (2,2 , 6,6-tetramethyl-4-piperidyloxy) ethane, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N′-diphenyl-1,4-phenylenediamine, N-phenyl-N′-cyclohexyl- 1,4-phenylenediamine and the like are included.

Examples of the phosphorus stabilizer (or antioxidant) include triisodecyl phosphite, trisnonyl phenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 2,2-methylene bis (4,6-di-). t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (branched C ₃ -C ₆ alkylphenyl) phosphite [e.g., tris ( 2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2- t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) -phenyl] phospho Sphite, tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite, etc.], bis (2-tert-butylphenyl) phenyl phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2 -t- butyl-4-phenylphenyl) phosphite, bis _(C 3 -C ₉ alkylaryl) pentaerythritol diphosphite [e.g., bis (2,4-di -t- butyl-4-methylphenyl) pentaerythritol Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.] , Triphenyl phosphate stabilizers (e.g., -Phenoxy-9-α- (4-hydroxyphenyl) -p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphapyro [5,5] undecane, tris (2,4-di-t- Butylphenyl) phosphate), diphosphonite stabilizers (for example, tetrakis (2,4-di-t-butyl) -4,4′-biphenylenediphosphonite) and the like. The phosphorus-based stabilizer usually has a branched C _{3 to} C ₆ alkylphenyl group (particularly a t-butylphenyl group).

Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone, and examples of the quinoline antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2. -Dihydroquinoline and the like are included, and sulfur-based antioxidants include, for example, dilauryl thiodipropionate, distearyl thiodipropionate, and the like.

  These antioxidants or stabilizers can be used alone or in combination of two or more. The blending amount of the antioxidant or stabilizer (F) is 0.1 to 1.0% by mass in the thermoplastic resin composition of the present invention, or the PAS from the point that the effect of preventing gas generation becomes remarkable. The amount is preferably 0.01 to 5 parts by mass, particularly preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total mass of the resin (A) and the aromatic polyamide.

  Furthermore, the thermoplastic resin composition of the present invention includes 1) phosphoric acids, phosphorous acids and hypophosphorous acids, 2) metal phosphates, metal phosphites, and the like as long as the effects of the present invention are not impaired. Metal salt of hypophosphite, and 3) one or more phosphorous compounds (G) selected from phosphoric acid compounds such as phosphoric acid esters and phosphorous acid esters, phosphorous acid compounds and hypophosphorous acid compounds are used in combination Suppresses thermal decomposition of the polymer component during the melt-kneading of the PAS resin (A) and the aromatic polyamide or during heat treatment of the molded product in a reflow furnace, and has excellent mechanical strength and flame retardancy. It is preferable from the standpoint that the improvement can be achieved and the effect of improving the appearance of the molded article after the heat treatment becomes more remarkable.

Examples of 1) phosphoric acid, phosphorous acid and hypophosphorous acid include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, diphosphorous acid and the like.
The metal phosphate, metal phosphite, and metal hypophosphite of 2) above are the phosphorus compound of 1) and Groups 1 and 2 of the periodic table, manganese, zinc, aluminum, ammonia, Mention may be made of salts with alkylamines, cycloalkylamines and diamines.
The phosphoric acid esters and phosphites of 3) are represented by the following general formula.
Phosphate ester; (OR) _n PO (OH) _3-n
Phosphite; (OR) _n P (OH) _3-n

Here, n represents 1, 2 or 3, and R represents an alkyl group, a phenyl group, or an alkyl group in which a part of these groups is substituted with a hydrocarbon group or the like. When n is 2 or more, a plurality of (RO) groups in the general formula may be the same or different.
As R, methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, nonyl group, decyl group, stearyl group, oleyl group And an aliphatic group such as an aliphatic group such as phenyl group and biphenyl group, or an aromatic group having a substituent such as hydroxyl group, methyl group, ethyl group, propyl group, methoxy group and ethoxy group. .

The preferred phosphorus compound of the present invention is at least one selected from metal phosphates, metal phosphites or metal hypophosphites. Among them, a salt of a phosphorus compound selected from phosphoric acid, phosphorous acid, and hypophosphorous acid and a metal selected from Groups 1 and 2 of the periodic table, manganese, zinc, and aluminum is more preferable. Preferably it is calcium hypophosphite.

  The compounding amount of the phosphorus compound is 0.1 to 1.0% by mass in the thermoplastic resin composition of the present invention, or the PAS resin (A) and the fragrance, from the viewpoint that the gas generation prevention effect becomes remarkable. It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of total mass of a group polyamide, and it is especially preferable that it is 0.1-2 mass parts.

Furthermore, the thermoplastic resin composition of the present invention is preferably blended so that the chlorine atom content contained in the heat-resistant resin composition is 900 ppm or less from the viewpoint of regulating the chlorine atom content. Here, the chlorine atom content contained in the heat-resistant resin composition is the chlorine atom content in a state in which not only the resin component but also all compounding components are contained. It can be performed by performing combustion (900 ° C., Ar—O ₂ atmosphere) in a sealed quartz tube, absorbing the generated gas in pure water, and measuring chloride ions by ion chromatography.

  Furthermore, the thermoplastic resin composition of the present invention includes a processing heat stabilizer, a plasticizer, a mold release agent, a colorant, a lubricant, a weathering stabilizer, a foaming agent, and an anticorrosive agent as long as the effects of the present invention are not impaired. An appropriate amount of an agent and wax may be added.

  Furthermore, the thermoplastic resin composition of the present invention may be appropriately blended with other resin components in accordance with required properties. Examples of the resin component that can be used here include ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) acrylonitrile, and the like. Monomer homopolymer or copolymer, Polyester such as polyurethane, polyester, polybutylene terephthalate, polyethylene terephthalate, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyphenylene ether, polyetherketone, polyether Single weight of ether ketone, polyimide, polyamideimide, polyetherimide, silicone resin, epoxy resin, phenoxy resin, liquid crystal polymer, polyaryl ether, etc. Body, a random copolymer or a block copolymer and a graft copolymer, and the like.

  Specifically, the method for producing the heat-resistant resin composition described in detail above includes the PAS resin (A) and the polyamide (B), wherein the polyamide (B) is 10 to 30 per 100 parts by mass of the total mass of the blending components. The ratio of the resin component discharge rate (kg / hr) to the screw rotation speed (rpm) (discharge amount / screw rotation speed) is 0.02 to 0.02. 2 (kg / hr · rpm), and a method of melt-kneading under the condition that the temperature of the discharged resin is in the range of 345 to 370 ° C.

At this time, the mixture is put into a twin-screw kneading extruder, and the production method will be described in more detail. PAS resin (A) and polyamide (B), and if necessary, other blending components are added using a tumbler or Henschel mixer. Mix evenly, then feed into twin screw extruder, set temperature 300 ° C,
A method of melt-kneading under a temperature condition of a resin temperature of about 360 ° C. can be mentioned.
At this time, the discharge amount of the resin component is in the range of 5 to 50 kg / hr at a rotational speed of 150 to 250 rpm. Especially, it is preferable that it is 10-30 kg / hr from a dispersible point. Therefore, the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is particularly 0.08 to 0.14 (kg / hr · rpm). Is preferred.

  In addition, the fibrous reinforcing material (E-1) among the above-mentioned blending components can be introduced into the extruder from the side feeder of the twin-screw extruder so that the dispersibility of the fibrous reinforcing material (E-1) is good. It is preferable from the point which becomes. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging part to the side feeder with respect to the total screw length of the biaxial extruder is 0.1 to 0.6. Among these, 0.2 to 0.4 is particularly preferable.

  The heat-resistant resin composition melt-kneaded in this manner is obtained as pellets, and then subjected to melt molding using a molding machine to obtain the desired molded product.

  Examples of the melt molding method include injection molding, extrusion molding, and compression molding. Among these, injection molding is particularly preferable for molding of electronic components for surface mounting.

  The molded product thus obtained is excellent in heat resistance and has a high elastic modulus in a high temperature range, and therefore can be preferably used for a molded product to be soldered. In particular, as described above, in the surface mount electronic component application, the surface temperature of the substrate in the heating furnace (reflow furnace) becomes a high temperature of 280 ° C. or higher, but the conventional PAS resin is melted or deformed. In contrast, the thermoplastic resin composition of the present invention can be soldered to the substrate without the molded article melting or deforming. The surface temperature of the substrate to be soldered is a temperature actually measured on the surface of the substrate in the soldering process in the surface mounting method. Specific examples of the substrate include printed circuit boards and circuit boards in the SMT method.

  Further, the heating method in the heating furnace (reflow furnace) in the surface mounting method described above includes (1) a heat conduction method in which a substrate is heated on a heat-resistant belt moving on the heater, and (2) about Vapor phase soldering (VPS) method using latent heat when a fluorine-based liquid having a boiling point of 220 ° C. is condensed, (3) Hot air convection heat transfer method through which hot air is forced to circulate, (4) Examples include an infrared method in which heating is performed from the upper or upper and lower surfaces of the substrate with infrared rays, and (5) a method using a combination of heating with hot air and heating with infrared rays.

  The molded article of the thermoplastic resin composition of the present invention can be used in a wide range of fields such as precision parts, various electrical / electronic parts, machine parts, automotive parts, architecture, sanitary, sports, miscellaneous goods, etc. Particularly, since it is excellent in flame retardancy, heat resistance, rigidity, etc., it is particularly useful as an electronic component for surface mounting as described above.

  Here, the electronic component for surface mounting according to the present invention has the above-described molded product of the heat-resistant resin composition and a metal terminal as essential components, and is printed on a printed circuit board or circuit board. It is fixed by the mounting method. In order to fix the electronic component to the substrate by the surface mounting method, the metal terminal of the electronic component is placed on the surface of the substrate so as to be in contact with the current-carrying portion on the substrate through the solder ball, and the inside of the reflow furnace is performed by the heating method described above. There is a method in which the electronic component is soldered to the substrate by heating at a temperature.

  Specific examples of such surface mounting electronic components include connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, IC and LED housings, and the like for surface mounting systems. It is done.

  In addition, the heat-resistant resin molded article obtained by the production method of the present invention does not contain a flame retardant such as so-called halogenated copper, antimony oxide or metal hydroxide, without adding a UL flame resistance test standard UL-94 (Underwriters). Laboratories, Incorporated, (UL) Standard No. 94) achieves high flame retardancy equivalent to V-0.

Hereinafter, the present invention will be described in more detail with reference to examples.
Examples 1-8 and Comparative Examples 1-4
According to the blending ratios described in Tables 1 and 2, polyarylene sulfide resin, polyamide and other blending materials (excluding glass fiber chopped strands) were uniformly mixed with a tumbler. Thereafter, the blended material was charged into a vented twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd., and the side feeder (the ratio of the distance from the resin charging portion to the side feeder relative to the total length of the screw: 0. 0). 28) while supplying a glass fiber chopped strand having a fiber diameter of 10 μm and a length of 3 mm at a rate of 40 parts by mass with respect to 60 parts by mass of the above compounded material, a resin component discharge rate of 15 kg / hr, a screw rotation speed of 150 rpm, a resin component Ratio (kg / hr) to screw rotation speed (rpm) (discharge volume / screw rotation speed) = 0.1 (kg / hr · rpm), maximum torque 53 (Å), set resin temperature 320 ° C. And kneaded to obtain pellets of the resin composition.
Next, various evaluation tests were performed using the pellets. The results are shown in Tables 1 and 2.
Each evaluation test method and property value evaluation method are as follows.

[Measurement of melt viscosity]
At 350 ° C., the melt viscosity at a shear rate of 100 sec ⁻¹ was measured with a capillary graph 1B manufactured by Toyo Seiki Seisakusho using a capillary with L / D = 40/1.

[How to determine the extraction rate of hexafluoroisopropanol]
The pellet of the composition is freeze-ground using a freeze-pulverizer, passed through a sieve having an opening of 500 μm, and then about 1 g of the ground sample is precisely weighed into a 20-ml sample tube, and 4 ml of hexafluoroisopropanol (HFIP) is added. Add. Next, the sample tube containing the sample and HFIP is sonicated with an ultrasonic cleaner at 70 ° C. for 15 minutes. Furthermore, the sonication liquid was quantitatively transferred to a filter with a precisely weighed mass and filtered. Then, the filter is dried and weighed, and the mass of the filtration residue is measured. The difference between the mass weighed before the treatment and the mass after drying (excluding the mass of the filter) is the mass of the extracted component, and the value obtained by dividing this by the mass weighed before the treatment is expressed as a percentage. The extraction rate.

[Combustion test]
A flame test was performed based on the UL-94 vertical test to evaluate flame retardancy.

[Measurement of chloro content]
The resin composition pellet is burned (900 ° C., Ar—O ₂ atmosphere) in a sealed quartz tube, the generated gas is absorbed in pure water, and chloride ions are quantified by ion chromatography to determine the amount of chloro contained. Calculated.
<Processing equipment>
Combustion gas absorber "AQF-100" manufactured by Dia Instruments
Ion chromatograph "ICS-3000" manufactured by Dionex

[Blister resistance test]
The resin composition pellets were molded using an injection molding machine to form a box connector having a shape of 50 mm long × 10 mm wide × 8 mm high and 0.8 mm thick. Next, the box connector was subjected to a reflow process using an infrared heating furnace (manufactured by Sanyo Seiko, SMT scope) according to the temperature profile shown in FIG. Evaluation was made by visually observing the box-shaped connector after heating, and evaluated according to the following two-stage criteria.
A: No change in appearance. B: Blister or melting was observed.

The compounded resins and materials in Tables 1 and 2 are as follows.
(1) PPS-1: Polyphenylene sulfide (“DSP LR-1G” manufactured by DIC Corporation; non-Newtonian index 1.1, peak molecular weight 28,000, Mw / Mn = 7.5, Na content 300 ppm, melt viscosity 35 Pa・ S)
(2) PPS-2: Linear polyphenylene sulfide (“LR-3G” manufactured by DIC Corporation; non-Newton index 1.2, peak molecular weight 34000, Mw / Mn = 7.6, Na content 300 ppm, melt viscosity 85 Pa · s)
(3) PA6T-1: aromatic polyamide obtained by reacting 65 mol% terephthalic acid, 25 mol% isophthalic acid and 10 mol% adipic acid as essential monomer components (melting point 312 ° C, weight average molecular weight 42000, melt viscosity 82Pa · s)
(4) PA6T-2: Aromatic polyamide (melting point 310 ° C., weight average molecular weight 33,000, melt viscosity) obtained by reacting 66 mol% terephthalic acid, 23 mol% isophthalic acid and 11 mol% adipic acid as essential monomer components 50 Pa · s)
(5) PA6T-3: Aromatic polyamide (melting point 320 ° C., weight average molecular weight 27000, melt viscosity) obtained by reacting 64 mol% terephthalic acid, 34 mol% isophthalic acid, and 2 mol% adipic acid as essential monomer components 45 Pa · s)
(6) PA46: polyamide obtained by reacting 50 mol% adipic acid and 50 mol% tetramethylenediamine as essential monomer components (melting point 293 ° C., weight average molecular weight 38000, melt viscosity 65 Pa · s)
(7) PA6T-4: Aromatic polyamide (melting point 308 ° C., weight average molecular weight 31000, melt viscosity) obtained by reacting terephthalic acid 52 mol%, isophthalic acid 3 mol%, and adipic acid 37 mol% as essential monomer components 29Pa · s)
(8) Si-1: Epoxysilane (γ-glycidoxypropyltrimethoxysilane)
(9) Si-2: 3-aminopropyltrimethoxysilane (10) Si-3: N-2 (aminoethyl) 3-aminopropyltriethoxysilane (11) Si-4: 3-isocyanatopropyltriethoxysilane ( 12) Si-5: 2- (3,4 epoxy cyclohexyl) trimethoxysilane (13) ADD-1: hindered phenol antioxidant (“Irganox 1098” manufactured by Ciba Specialty Chemicals Co., Ltd.)
(14) ADD-2: Phosphorus-based processing heat stabilizer bis (“ADEKA STAB PEP-36” manufactured by ADEKA Corporation; 2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite)
(15) ADD-3: Hydrotalcite (“DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd.)
(16) GF: Glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

Claims (15)

  A resin composition comprising a polyarylene sulfide resin (A) and a polyamide (B) as essential components, wherein the content of the polyamide (B) per 100 parts by mass of the composition is 10 to 30 parts by mass. And the extraction rate at the time of extracting this composition with hexafluoroisopropanol at 70 degreeC for 15 minute (s) is 7 mass% or less, The thermoplastic resin composition characterized by the above-mentioned.   The thermoplastic resin composition according to claim 1, wherein the polyamide (B) has a melting point in the range of 280 to 330 ° C.   The content of the polyamide (B) per 100 parts by mass of the resin composition containing the polyarylene sulfide resin (A) and the polyamide (B) as essential components is X (mass%), and the composition is hexafluoroisopropanol. The thermoplastic resin composition according to claim 1, wherein the value of Y / X is in the range of 0.01 to 0.40, where Y (mass%) is the extraction rate when extracted at 70 ° C for 15 minutes. When the melt viscosity of the polyarylene sulfide resin (A) is η _A and the melt viscosity of the polyamide (B) having a melting point in the range of 280 to 330 ° C. is η _{B under} the shear rate conditions of 350 ° C. and 100 sec ^−1. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the value of η _B / η _A is 0.9 to 5.0.   In addition to the polyarylene sulfide resin (A) and the polyamide (B) having a melting point in the range of 280 to 330 ° C., the reactive functional group-containing organosilane (C) is added in an amount of 0.01 to 100 parts by mass per 100 parts by mass of the composition. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition is contained in a proportion of 2 parts by mass.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the polyarylene sulfide resin (A) has a Na content of 1,000 ppm or less. The polyamide (B) has the following structural formula a

(In the formula, R ¹ represents an alkylene group having 2 to 12 carbon atoms.)
The terephthalic acid amide structure (a) represented by the formula: 65 to 75 mol%, the following structural formula b

(In the formula, R ¹ represents an alkylene group having 2 to 12 carbon atoms.)
20 to 25 mol% of the isophthalic acid amide structure (b) represented by the formula:

(In the formula, R ¹ represents an alkylene group having 2 to 12 carbon atoms, and R ² represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms.)
The thermoplastic resin composition according to any one of claims 1 to 6, which has an aliphatic hydrocarbon structure (c) represented by formula (5) at a ratio of 5 to 15 mol%.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the polyamide (B) is an aliphatic polyamide having 2 to 4 carbon atoms in the aliphatic hydrocarbon moiety.   The thermoplastic resin composition according to claim 5, wherein the reactive functional group in the reactive functional group-containing organosilane (C) is at least one selected from an epoxy group, an amino group, and an isocyanate group.   The fiber reinforcing material (E-1) or inorganic filler (E-2) is contained in a proportion of 5 to 50 parts by mass per 100 parts by mass of the composition in addition to the above components. The thermoplastic resin composition according to any one of claims.   The polyarylene sulfide resin (A) and the polyamide (B) are charged into the twin-screw kneading extruder at a ratio of 10 to 30 parts by mass of the polyamide (B) per 100 parts by mass of the total mass of all the ingredients. The ratio of the resin component discharge rate (kg / hr) to the screw speed (rpm) (discharge rate / screw speed) is 0.02 to 0.2 (kg / hr · rpm) A method for producing a thermoplastic resin composition, comprising melt-kneading under conditions where a temperature is in a range of 345 to 370 ° C.   The method for producing a thermoplastic resin composition according to claim 11, wherein the polyamide (B) has a melting point in the range of 280 to 330 ° C.   In addition to the polyarylene sulfide resin (A) and the polyamide (B), the reactive functional group-containing organosilane (C) is used at a ratio of 0.01 to 2 parts by mass per 100 parts by mass of the total mass of the ingredients. The manufacturing method of the thermoplastic resin composition of Claim 11 or 12.   The fiber reinforcing material (E-1) or inorganic filler (E-2) is used in a proportion of 5 to 50 parts by mass per 100 parts by mass of the total mass of the blending components in addition to the above components. The manufacturing method of the thermoplastic resin composition of any one of Claims.   An electronic component for surface mounting comprising the molded product of the thermoplastic resin composition according to any one of claims 1 to 10 and a metal terminal as essential components.

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