JP2015178590A - Polyphenylene sulfide resin composition and molded article containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition excellent in flowability and dimension stability and achieving high strength by improving adhesiveness with a filler, and a molded article containing the same.SOLUTION: A polyphenylene sulfide resin composition of the present invention contains 100 pts.wt. of (A) polyphenylene sulfide resin and 1 to 30 pts.wt. of (B) mica having linseed oil absorption amount (according to JISK5101-13-2(2004)) of 67 ml/100 g to 90 ml/100 g.

Description

  The present invention relates to a polyphenylene sulfide resin composition that is excellent in fluidity and dimensional stability, and has achieved high strength through improved adhesion to a filler, and a molded article comprising the same.

  Polyphenylene sulfide (hereinafter may be abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, electrical insulation, and heat and humidity resistance, with a focus on injection molding and extrusion molding. It is used for various electric / electronic parts, machine parts and automobile parts.

  In general, in order to apply to high dimensional precision parts such as electrical and electronic parts, it is necessary to improve material rigidity and dimensional stability without anisotropy due to filler orientation. A method of blending mica from the viewpoint is often used. However, since mica has a small reinforcing effect as compared with fibrous fillers such as glass fibers, there are problems such as a decrease in molding processability due to low fluidity in order to mix in a large amount. Therefore, a mica-blended PPS resin material having high fluidity, high dimensional stability, and high strength is strongly desired.

  So far, several reports have been made on resin compositions in which mica is blended with PPS resin.

  For example, Patent Document 1 discloses a resin composition in which mica having an aspect ratio of 80 or more is blended with polyphenylene sulfide resin, but a relatively small amount of mica having a linseed oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less is added. By doing so, there is no description about the improvement in adhesion to the filler and the development of high strength.

  Patent Document 2 discloses a resin composition in which mica having an aspect ratio of 20 or more is blended with a synthetic resin having a melting temperature of 300 ° C. or higher. Linseed oil absorption is 67 ml / 100 g or more and 90 ml / 100 g or less. There is no description of the fact that the addition of a relatively small amount of mica improves the adhesion to the filler and develops high strength.

  Patent Document 3 discloses a resin composition comprising a polyphenylene sulfide resin, an amorphous thermoplastic resin having a glass transition temperature of 120 ° C. or higher, an admixture, and an inorganic filler, but the mica used in the examples is disclosed. There is no description of the oil absorption amount, and there is no description about the fact that the linseed oil absorption amount of 67 ml / 100 g or more and 90 ml / 100 g or less of mica is mixed in a relatively small amount, thereby improving the adhesion with the filler and increasing the strength. It has not been.

  In addition, by adding an alkoxysilane compound having at least one group selected from an epoxy group, an amino group, and an isocyanate group to any of Patent Documents 1 to 3, adhesion to the filler is further improved, and the machine No mention is made of improving the strength.

International Publication No. 2013/080566 (Claims, Examples) International Publication No. 01/40380 (Claims, Examples) JP 2004-268391 A (Claims, Examples)

  An object of the present invention is to obtain a polyphenylene sulfide resin composition that is excellent in fluidity and dimensional stability, and has achieved high strength by improving adhesion with a filler, and a molded product comprising the same.

  Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors incorporated a specific mica having a linseed oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less into the PPS resin. Since the adhesiveness with the filler is improved, it has been found that a PPS resin composition having high dimensional stability and high strength can be obtained without impairing fluidity, and the present invention has been achieved.

That is, the present invention is as follows.
1. (A) The linseed oil absorption (based on JISK5101-13-3 (2004)) is 67 ml / 100 g or more and 90 ml / 100 g or less with respect to 100 parts by weight of the polyphenylene sulfide resin (B) 1-30 parts by weight of mica A polyphenylene sulfide resin composition comprising:
2. (A) 1 to 30 parts by weight of an alkoxysilane compound having at least one group selected from an epoxy group, an amino group and an isocyanate group is blended with 100 parts by weight of polyphenylene sulfide. 2. The polyphenylene sulfide resin composition according to 1.
3. (B) The polyphenylene sulfide resin composition according to any one of 1 and 2, wherein the volume average particle diameter of the mica is 5 μm or more and 10 μm or less.
4). (A) To 100 parts by weight of polyphenylene sulfide resin, 0.05 to 5 parts by weight of (D) an ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol is contained. The polyphenylene sulfide resin composition according to any one of 1 to 3, wherein
5. (A) The polyphenylene sulfide resin composition according to any one of 1 to 4, comprising 1 to 50 parts by weight of (E) fibrous filler with respect to 100 parts by weight of polyphenylene sulfide.
6.1 A molded article comprising the polyphenylene sulfide resin composition according to any one of 1 to 5.
It is.

  According to the present invention, since the interfacial adhesion between the resin and the filler is drastically improved by blending specific mica having a linseed oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less, a large amount of mica is blended. Since there is no need, a PPS resin composition excellent in dimensional stability and mechanical strength can be obtained without impairing fluidity and material specific gravity. Moreover, since the molded product obtained from the polyphenylene sulfide resin composition of the present invention is excellent in surface smoothness, it is useful as an automobile exterior product that requires metal plating treatment or coating treatment.

  Moreover, the PPS resin composition of the present invention is further excellent in releasability by further blending (D) an ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol, and A PPS resin composition having excellent mold fouling properties can be obtained.

It is a figure which shows the shape of the metal mold | die used for the release property evaluation of the small box shape in an Example. It is a figure which shows the shape of the metal mold | die used for the mold release property evaluation of the cylindrical shape in the Example. It is a figure which shows the temperature profile used for the surface mounting IR reflow test in the Example. It is a figure which shows the shape of the metal mold | die used for metal mold | die stain | pollution | contamination evaluation in the Example.

  Hereinafter, embodiments of the present invention will be described in detail.

(A) Polyphenylene sulfide resin Specifically, it is a homopolymer or copolymer having a repeating unit of the formula:-(Ar-S)-as the main constituent unit, preferably containing 80 mol% or more of the repeating unit, and Ar Are units represented by the following formulas (a) to (k), among which the formula (a) is particularly preferable.

  (R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group, and R1 and R2 May be the same or different)

  As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (l) to (n). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S)-units.

  The (A) PPS resin used in the present invention may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. In particular, from the viewpoint of low gas and high heat resistance, the (A) PPS resin used more preferably includes a p-phenylene sulfide unit as the main structural unit of the polymer.

Is a polyphenylene sulfide resin containing 80 mol% or more, particularly 90 mol% or more.

  In the present invention, as the (A) PPS resin, an (A ′) PPS resin that can be obtained by, for example, a production method described later and that is more excellent in retention stability can also be used.

  The melt viscosity of the (A) PPS resin used in the present invention is not limited, but is preferably 300 Pa · s (300 ° C., shear rate 1000 / s) or less from the viewpoint of easily obtaining a thin injection molded product. 200 Pa · s or less is more preferable, and 100 Pa · s or less is more preferable. The lower limit is preferably 1 Pa · s or more from the viewpoint of melt molding processability and gas generation amount. The melt viscosity in the present invention is a value measured by using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.

The (A) PPS resin having the above-mentioned melt viscosity can be exemplified as a preferable range in which the melt viscosity change rate defined by the following formula (1) is 30% or less from the viewpoint of melt residence stability at the time of molding, 25% The following is more preferable, and 20% or less is more preferable.
Melt viscosity change rate (%) = 100 (ηa / ηb-1) (1)

  In addition, among (A) PPS resins, (A ′) PPS resins that are more excellent in melt residence stability can be exemplified by a melt viscosity change rate of preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. preferable. Here, ηa in the above equation was measured using a Toyo Seiki Capillograph under the conditions of a measurement temperature of 300 ° C., a residence time of 5 minutes, an orifice L / D = 10 mm / 1 mm, a shear rate of 10 to 6000 / s, and an oxygen atmosphere. It represents the initial melt viscosity (Pa · s) of polyphenylene sulfide, and ηb represents the melt viscosity (Pa · s) after melt residence measured under the same conditions as ηa except that the residence time was changed to 30 minutes.

  When the melt viscosity change rate is 15% or less, it is particularly suitable for injection molding of a large number of large-sized automobile parts with a relatively long melt residence time, and product defects (short shots and overfilling) due to fluidity variations It is also advantageous in terms of productivity because it can be controlled and the molding yield rate (the amount of material used to produce the required number of products / the amount of material actually used × 100) can be as close as possible to 100%. It is.

  The lower limit of the molecular weight (weight average molecular weight) of the (A) PPS resin of the embodiment of the present invention is selected in the range of 10,000 or more, preferably 15000 or more, more preferably 18000 or more. In addition, the upper limit value of the molecular weight (weight average molecular weight) of the (A) polyphenylene sulfide resin is selected within a range of 100,000 or less, preferably 50000 or less, and more preferably 30000 or less. (A) If the lower limit value of the weight average molecular weight of the polyphenylene sulfide resin is less than 10,000, the gas generation amount increases during the molding process, the moldability is lowered, and the mechanical strength of the molded product is also impaired. However, if the upper limit of the weight average molecular weight exceeds 100,000, solidification in the mold is slowed down, so that the molded product does not crystallize sufficiently, and a sufficient heat resistance improvement effect cannot be obtained. there is a possibility. When the weight average molecular weight of the (A) polyphenylene sulfide resin of the embodiment of the present invention is smaller, the resin in the mold is solidified faster, and a dramatic heat resistance improvement effect due to high crystallization of the molded product is manifested.

  In the embodiment of the present invention, (A) the molecular weight distribution of the PPS resin is broadened, that is, the degree of dispersion represented by the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is preferably 5.0 or less, 4.0 or less is preferable and 3.0 or less is more preferable. Among the (A) PPS resins, the (A ′) PPS resin has a particularly narrow molecular weight distribution, the dispersity is preferably 2.5 or less, more preferably 2.3 or less, and further preferably 2.1 or less, 2.0 or less is even more preferable. When the degree of dispersion is 2.5 or less, the amount of low molecular weight components contained in the PPS resin is extremely small. This is an improvement in mechanical properties when the PPS resin is used for molding processing, and the amount of gas generated when heated. It shows that the tendency of the decrease in the amount of elution and the decrease in the amount of the eluted component when in contact with the solvent is remarkable. The weight average molecular weight and the number average molecular weight can be determined using, for example, SEC (Size Exclusion Chromatography) equipped with a differential refractive index detector.

  The alkali metal content, which is an impurity contained in the (A) PPS resin used in the present invention, is not particularly limited, but the alkali metal content is expressed as a weight ratio from the viewpoint of developing applications for electrical and electronic parts that require electrical insulation. A preferable range is less than 1500 ppm. An alkali metal content of 1500 ppm or more is not preferable because problems such as a decrease in electrical insulation due to metal impurities occur. In addition, it is preferable to use (A ′) PPS resin in order to develop semiconductor encapsulated parts that have strict requirements for electrical insulation, and (A ′) alkali metal content of PPS resin from the viewpoint of lowering electrical insulation described above. The amount can be exemplified as a preferable range by weight ratio of less than 700 ppm, and more preferably less than 100 ppm. The alkali metal content here is, for example, a value calculated from the amount of alkali metal in ash that is a residue obtained by baking (A) PPS resin using an electric furnace or the like. It can be quantified by analyzing by an atomic absorption method.

  The alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium belonging to Group IA of the periodic table, but the (A) polyphenylene sulfide resin of the present invention does not contain an alkali metal other than sodium. Is preferred. When an alkali metal other than sodium is included, it tends to adversely affect the electrical characteristics and thermal characteristics of the polyphenylene sulfide resin composition. In addition, there is a possibility that the amount of eluted metal when the (A) polyphenylene sulfide resin comes into contact with various solvents is increased, and this tendency is particularly strong when the (A) polyphenylene sulfide resin contains lithium. By the way, among various metal species, compared to metal species other than alkali metals, such as alkaline earth metals and transition metals, alkali metals have an effect on the electrical properties, thermal properties, and metal elution amount of polyphenylene sulfide resin compositions. Tend to be strong. Therefore, it is estimated that the quality of (A) polyphenylene sulfide resin can be improved by making alkali metal content into the said range especially among various metal seed | species.

The (A ′) PPS resin used in the embodiment of the present invention is particularly characterized in that the amount of gas generation is smaller than that of the (A) PPS resin, and the weight reduction rate when heated satisfies the following formula (1).
ΔWr = (W1-W2) /W1×100≦0.18 (%) (1)
Here, ΔWr is a weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature increase rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure. The value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.

  (A ′) The weight reduction rate of the PPS resin is such that ΔWr is 0.18% or less, preferably 0.12% or less, more preferably 0.10% or less, and 0.085%. It is even more preferable that: If △ Wr exceeds the above range, for example, there is a tendency that problems such as restriction of application development to precision electrical / electronic parts that require extremely low gasity tend to occur, and the mechanical strength of the molded product decreases. This is not preferable because of the tendency to

  ΔWr can be obtained by a general thermogravimetric analysis, and the atmosphere in this analysis is a normal pressure non-oxidizing atmosphere. The non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the sample is 5% by volume or less, preferably 2% by volume or less, and more preferably an oxygen-free atmosphere, that is, inert such as nitrogen, helium, argon, etc. Indicates a gas atmosphere.

  Among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. The normal pressure is a pressure in the vicinity of the standard state of the atmosphere, and is an atmospheric pressure condition in which the temperature is about 25 ° C. and the absolute pressure is about 101.3 kPa. If the measurement atmosphere is other than the above, the PPS resin may be oxidized during the measurement, or may differ greatly from the atmosphere actually used in the molding process of the PPS resin. There is no possibility.

  In the measurement of ΔWr, thermogravimetric analysis is performed by increasing the temperature from 50 ° C. to an arbitrary temperature of 330 ° C. or higher at a temperature increase rate of 20 ° C./min. Preferably, after holding at 50 ° C. for 1 minute, the temperature is increased at a rate of temperature increase of 20 ° C./min to perform thermogravimetric analysis. This temperature range is a temperature region frequently used when the polyphenylene sulfide resin is actually used, and is also a temperature region frequently used when the solid PPS is melted and then molded into an arbitrary shape. The weight reduction rate in the actual use temperature region is related to the amount of gas generated from the PPS resin during actual use, the amount of components adhering to the die or mold during molding, and the like. Therefore, it can be said that a PPS resin having a lower weight loss rate in such a temperature range is an excellent PPS resin having a higher quality. It is desirable to measure ΔWr with a sample amount of about 10 mg mg, and the shape of the sample is desirably a fine particle of about 2 mm or less.

  Although the reason why the weight loss rate during heating of the (A ′) PPS resin used in the embodiment of the present invention satisfies the above formula (1) is not clearly understood, it is not clear at present. The (A ′) PPS resin used in this embodiment is presumed to be effective in that the content of impurity components other than the PPS component is small, and to exhibit a significantly low weight reduction rate.

  Thus, the (A ′) PPS resin having the characteristics of the above formula (1) is produced by heating a polyphenylene sulfide prepolymer containing cyclic polyphenylene sulfide and converting it to a high degree of polymerization as described later. Is preferred. Although the conversion to a high polymerization degree will be described in detail later, the weight fraction of the cyclic PPS contained in the PPS resin obtained after the operation of converting the polyphenylene sulfide prepolymer to the high polymerization degree is 40. % Or less, preferably 25% or less, more preferably 15% or less, is preferable because the above-described ΔWr value is particularly small. Weight fraction of cyclic PPS When this value exceeds the above range, the value of ΔWr tends to increase. The cause of this is not clear at present, but the cyclic PPS contained in the PPS resin is partially heated. It is presumed to volatilize.

  In addition, when the weight reduction rate when heated, which is a characteristic of the (A ′) polyphenylene sulfide resin used in the present invention, satisfies the above formula (1), the range of the weight average molecular weight and dispersity of the (A ′) PPS resin And / or the condition selected from the alkali metal content is not necessarily within the above-mentioned range, and as described above, the PPS resin containing a certain amount of cyclic PPS or the like can also have the thermal weight of the formula (1). It is possible to satisfy the characteristics. However, when the range of the weight average molecular weight and the degree of dispersion of the PPS resin is within the above range, and / or when the condition selected from the alkali metal content of the PPS is within the above range, This is desirable because weight loss tends to be particularly small.

  As described above, the (A ′) PPS resin used in the embodiment of the present invention has an excellent feature that the weight loss rate reduction ΔWr at the time of heating is small, but at any given constant temperature ( A ′) When holding the PPS resin, there is a tendency to have an excellent feature that the weight reduction rate (heating loss) compared before and after heating is small.

  The (A ′) PPS resin used in the present invention also has a feature that the amount of lactone-type compound and / or aniline-type compound generated when heated is significantly less than that of (A) PPS resin. Examples of the lactone type compound include β-propiolactone, β-butyrolactone, β-pentanolactone, β-hexanolactone, β-heptanolactone, β-octanolactone, β-nonalactone, and β-decalactone. , Γ-butyrolactone, γ-valerolactone, γ-pentanolactone, γ-hexanolactone, γ-heptanolactone, γ-octalactone, γ-nonalactone, γ-decalactone, δ-pentanolactone, δ-hexa Examples include nolactone, δ-heptanolactone, δ-octanolactone, δ-nonalactone, and δ-decalactone. The aniline type compounds are aniline, N-methylaniline, N, N-dimethylaniline, N-ethylaniline, N-methyl-N-ethylaniline, 4-chloro-aniline, 4-chloro-N-methyl. Aniline, 4-chloro-N, N-dimethylaniline, 4-chloro-N-ethylaniline, 4-chloro-N-methyl-N-ethylaniline, 3-chloro-aniline, 3-chloro-N-methylaniline, Examples include 3-chloro-N, N-dimethylaniline, 3-chloro-N-ethylaniline, and 3-chloro-N-methyl-N-ethylaniline.

  The occurrence of lactone type compounds and / or aniline type compounds when heating PPS resin not only deteriorates the moldability but also causes contamination of the surrounding environment due to factors such as resin foaming and mold contamination during molding. The amount of lactone type compound generated in the PPS resin is preferably 500 ppm based on the weight of the PAS before heating. Hereinafter, 300 ppm, more preferably 100 ppm or less, and even more preferably 50 ppm or less is more desirable. Similarly, the amount of aniline-type compound generated is preferably 300 ppm or less, more preferably 100 ppm, still more preferably 50 ppm or less, and still more preferably 30 ppm or less. In addition, as a method for evaluating the generation amount of the lactone type compound and / or the aniline type compound when the PAS resin is heated, the gas generated after the treatment at 320 ° C. for 60 minutes in a non-oxidizing atmosphere is subjected to gas chromatography. An example is a method of quantifying the components by using them.

  Although the reason why the amount of these compounds generated during the heating of the (A ′) PPS resin used in the present invention is less than that of the (A) PPS resin is not clear at present, the polyphenylene sulfide prepolymer used in the preferred production method described later is a cyclic polyphenylene. It is presumed that the high purity containing at least 50% by weight of sulfide contributes to the low content of impurities that generate lactone type compounds and / or aniline type compounds when heated.

  Although the manufacturing method of (A) PPS resin used for this invention is demonstrated below, if (A) PPS resin of the said structure is obtained, it will not be limited to the following method.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
A polyhalogenated aromatic compound refers to a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa Polyhalogenated aroma such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds, and preferably p-dichlorobenzene is used. Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

  The polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95 to 1. mol per mol of sulfiding agent, from the viewpoint of obtaining a (A) PPS resin having a viscosity suitable for processing. A range of 5 moles, more preferably 1.005 to 1.2 moles can be exemplified.

[Sulfiding agent]
Examples of the sulfiding agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  In addition, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

  Alternatively, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  The amount of the sulfidizing agent charged means a residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
An organic polar solvent is preferably used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. Of these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

  The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol per mol of the sulfidizing agent.

[Molecular weight regulator]
A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound for the purpose of forming the terminal of the (A) PPS resin to be produced or adjusting the polymerization reaction or molecular weight. Can be used together.

[Polymerization aid]
In order to obtain the (A) PPS resin having a relatively high degree of polymerization in a shorter time, it is one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means a substance having an action of increasing the viscosity of the obtained (A) PPS resin. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferable. Further, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides.

  The alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.

  The alkali metal carboxylate is an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, and are allowed to react by adding approximately equal chemical equivalents. You may form by. Among the alkali metal carboxylates, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in the polymerization system, is most preferably used.

  When using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, 0.6 to The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be obtained in a smaller amount.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient. Conversely, if the ratio is too large, it is economically disadvantageous or the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. It is more preferable because it is easy to add at the start of the process or at the start of the polymerization.

  Next, a preferred method for producing the (A) PPS resin used in the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process. Of course, the process is limited to this process. It is not something.

[pre-process]
(A) In the production method of PPS resin, the sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing agent is increased. It is preferable to warm and remove excess water out of the system.

  As described above, a sulfidizing agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidizing agent. Can do. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, there is a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 moles per mole of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
The (A) PPS resin is produced by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

  When starting the polymerization reaction step, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° C. . A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.

  The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

  In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is usually carried out at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 degreeC, the range of 0.25 to 20 hours is normally selected, Preferably the range of 0.25 to 10 hours is selected.

  In order to obtain a polymer having a higher degree of polymerization, it may be effective to perform polymerization in multiple stages. When the polymerization is performed in a plurality of stages, it is effective that the conversion of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (herein abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(1) When polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(2) In cases other than (1) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
(A) In the method for producing a PPS resin, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. Any known method may be adopted as the recovery method.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. It is not necessary to perform slow cooling at the same rate in the entire process of the slow cooling step, such as a method of gradually cooling at a rate of 0.1 to 1 ° C / min until the polymer particles are crystallized and precipitated, and then at a rate of 1 ° C / min or more. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery. This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually in the range of 150 ° C to 250 ° C.

[Post-processing process]
(A) The PPS resin may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment after being produced through the above polymerization and recovery steps.

  When acid treatment is performed, it is as follows. (A) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have an action of decomposing the (A) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the (A) PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing the (A) PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated (A) PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the (A) PPS resin by acid treatment is not impaired.

  When performing hot water treatment, it is as follows. (A) In the hot water treatment of the PPS resin, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 degreeC, since the effect of the preferable chemical modification | denaturation of (A) PPS resin is small, it is not preferable.

  The water used is preferably distilled water or deionized water in order to develop a preferable chemical modification effect of the (A) PPS resin by hot water washing. There are no particular restrictions on the operation of the hot water treatment, and a predetermined amount of (A) PPS resin is charged into a predetermined amount of water, heated and stirred in a pressure vessel, or continuously subjected to hot water treatment. Is called. (A) The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of (A) PPS resin of 200 g or less is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Furthermore, it is preferable that the (A) PPS resin which has finished this hot water treatment operation is washed several times with warm water in order to remove remaining components.

  When washing with an organic solvent, it is as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing the (A) PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as trachlorethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and the like Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like can be mentioned. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing the (A) PPS resin in an organic solvent, and stirring or heating can be appropriately performed as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (A) PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning for 5 minutes or more. It is also possible to wash in a continuous manner.

  As a method of treating alkali metal or alkaline earth metal, before the previous step, during the previous step, after the previous step, a method of adding an alkali metal salt or alkaline earth metal salt, before the polymerization step, during the polymerization step, during the polymerization step Examples include a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization vessel later, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle or last stage of the washing step. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers or residual salts by washing with an organic solvent or washing with warm water or hot water. Alkali metals and alkaline earth metals are preferably introduced into PPS in the form of alkali metal ions such as acetates, hydroxides and carbonates, and alkaline earth metal ions. It is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water. The concentration of alkali metal ions and alkaline earth metal ions when introducing the alkali metal and alkaline earth metal is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative to 1 g of PPS. As temperature, 50 degreeC or more is preferable, 75 degreeC or more is more preferable, and 90 degreeC or more is especially preferable. Although there is no upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and still more preferably 5 or more.

  In the present invention, from the viewpoint of improving the appearance of the molded product, residual oligomers that cause fogging, surface sticking, etc. are removed by repeating organic solvent washing and warm water of about 80 ° C. or hot water washing described above several times. The method is preferred. Further, from the viewpoint of improving the reactivity with the alkoxysilane compound having an isocyanate group (C) which is a compatibilizing agent, an acid treatment method is preferred.

  In addition, the (A) PPS resin can be used after being polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation crosslinking treatment by heating with addition of a crosslinking agent such as peroxide.

  When the dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. The oxygen concentration is preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In addition, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In order to obtain excellent surface smoothness and heat resistance, the (A) PPS resin used in the present invention comprises a high-molecular-weight PPS resin and a linear PPS resin with a small amount of residual oligomers, which are excellent in high-temperature rigidity. It may be used as a mixture, or a plurality of (A) PPS resins having different melt viscosities may be mixed and used.

  As the PPS resin used in the present invention, in addition to the method for producing (A) PPS resin which requires the above pre-process, polymerization reaction process, recovery process and post-treatment process, a production method as described below is used. It is possible to obtain a more preferable (A ′) PPS resin, but it is of course not limited to this method. It is also possible to use a mixture of the (A) PPS resin and the (A ′) PPS resin.

  As a method for producing the (A ′) PPS resin of the embodiment of the present invention, a polyphenylene sulfide prepolymer containing at least 50% by weight of cyclic polyphenylene sulfide and having a weight average molecular weight of less than 10,000 is heated to obtain a weight average. An example is a method of production by converting to a high degree of polymerization having a molecular weight of 10,000 or more. According to this method, the (A ′) PPS resin used in the embodiment of the present invention having the above-described characteristics can be easily obtained.

<Cyclic polyphenylene sulfide>
The cyclic polyphenylene sulfide in the preferred production method of the (A ′) polyphenylene sulfide resin used in the embodiment of the present invention is a cyclic represented by an integer of m = 4 to 20 represented by the following general formula (I). Polyphenylene sulfide (hereinafter sometimes abbreviated as cyclic PPS) can be used. Here, m is an integer of 4 to 20, and the cyclic polyphenylene sulfide to be used may be a mixture of plural types of cyclic polyphenylene sulfide having different m of 4 to 20.

  The cyclic polyphenylene sulfide may be either a single compound having a single repeating number or a mixture of cyclic polyphenylene sulfides having different repeating numbers. However, a mixture of cyclic polyphenylene sulfides having different numbers of repetitions tends to have a lower melting temperature than a single compound having a single number of repetitions, and use of a mixture of cyclic polyphenylene sulfides having different numbers of repetitions. Is preferable because the temperature at the time of conversion to a high degree of polymerization described later can be further reduced.

<Polyphenylene sulfide prepolymer>
A preferred method for producing the (A ′) polyphenylene sulfide resin used in the embodiment of the present invention is characterized in that the polyphenylene sulfide prepolymer containing the cyclic polyphenylene sulfide as described above is heated to be converted into a high degree of polymerization. The polyphenylene sulfide prepolymer used here contains at least 50% by weight of cyclic polyphenylene sulfide, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. preferable. The upper limit of the content of cyclic polyphenylene sulfide contained in the polyphenylene sulfide prepolymer is not particularly limited, but 98% by weight or less can be exemplified as a preferable range. Usually, the higher the weight ratio of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer, the higher the polymerization degree and melt viscosity of the PPS obtained after heating. That is, in the method for producing a polyphenylene sulfide resin (A ′) according to the embodiment of the present invention, the polymerization degree and melt viscosity of the obtained PPS can be easily adjusted by adjusting the abundance ratio of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer. It is possible to adjust to. In addition, when the weight ratio of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer exceeds the above upper limit, the melting temperature of the polyphenylene sulfide prepolymer tends to increase. Therefore, the weight of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer It is preferable to set the ratio in the above range because the temperature when the polyphenylene sulfide prepolymer is converted into a high degree of polymerization can be further lowered.

  The component other than cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer is particularly preferably a linear polyphenylene sulfide oligomer. Here, the linear polyphenylene sulfide oligomer is a homo-oligomer or co-oligomer having a repeating unit of the formula:-(Ar-S)-as the main constituent unit, preferably containing 80 mol% or more of the repeating unit. . Ar includes units represented by the above-described formulas (a) to (k), among which the formula (a) is particularly preferable. The linear polyarylene sulfide oligomer may contain a small amount of branching units or crosslinking units represented by the above formulas (l) to (n) as long as these repeating units are the main constituent units. The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S)-units. The linear polyphenylene sulfide oligomer may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Examples of components other than cyclic polyphenylene sulfide include polyphenylene sulfide oligomers, polyphenylene sulfide sulfone oligomers, polyphenylene sulfide ketone oligomers, random copolymers, block copolymers, and mixtures thereof. It is done. Particularly preferred linear polyphenylene sulfide oligomers include linear polyphenylene sulfide oligomers containing 80 mol% or more, particularly preferably 90 mol% or more of p-phenylene sulfide units as the main structural unit of the polymer.

  The amount of linear polyphenylene sulfide contained in the polyphenylene sulfide prepolymer is particularly preferably smaller than the cyclic polyphenylene sulfide contained in the polyphenylene sulfide prepolymer. That is, the weight ratio of cyclic polyphenylene sulfide to linear polyphenylene sulfide (cyclic polyphenylene sulfide / linear polyarylene sulfide) in the polyphenylene sulfide prepolymer is preferably 1 or more, more preferably 2.3 or more, and more preferably 4 or more. Is more preferable, and 9 or more is even more preferable. In addition, by using such a polyphenylene sulfide prepolymer, it is possible to easily obtain a polyphenylene sulfide having a weight average molecular weight of 10,000 or more. Accordingly, the larger the weight ratio of the cyclic polyphenylene sulfide and the linear polyphenylene sulfide in the polyphenylene sulfide prepolymer, the higher the weight average of PPS obtained by the preferred method for producing the polyphenylene sulfide resin (A ′) of the embodiment of the present invention. The molecular weight tends to increase, so there is no particular upper limit to this weight ratio, but in order to obtain a polyphenylene sulfide prepolymer having a weight ratio exceeding 100, the content of linear PPS in the polyphenylene sulfide prepolymer is significantly reduced. This requires a lot of effort. According to the preferred method for producing the (A ′) polyphenylene sulfide resin of the embodiment of the present invention, it is possible to easily obtain a sufficient high molecular weight PPS even if a polyphenylene sulfide prepolymer having a weight ratio of 100 or less is used. .

  The upper limit of the molecular weight of the polyphenylene sulfide prepolymer used in the preferred method for producing the (A ′) polyphenylene sulfide resin used in the embodiment of the present invention is less than 10,000 in terms of weight average molecular weight, preferably 5,000 or less. Is more preferable. On the other hand, the lower limit is preferably 300 or more, preferably 400 or more, and more preferably 500 or more in terms of weight average molecular weight.

  The (A ′) polyphenylene sulfide resin used in the embodiment of the present invention is characterized by high purity, and the polyphenylene sulfide prepolymer used for production is also preferably high purity. Therefore, in the polyphenylene sulfide prepolymer, the content of alkali metal as an impurity is preferably less than 700 ppm by weight, more preferably 500 ppm or less, and even more preferably 300 ppm or less. In the production of the polyphenylene sulfide resin (A ′) used in the embodiment of the present invention, when a method of heating the polyphenylene sulfide prepolymer to convert it to a high degree of polymerization is used, the alkali metal content of the obtained PPS is usually Since it depends on the alkali metal content of the polyphenylene sulfide prepolymer, when the alkali metal content of the polyphenylene sulfide prepolymer exceeds the above range, the alkali metal content of the obtained PPS is (A ′) polyphenylene of the embodiment of the present invention. There is a risk of exceeding the alkali metal content range of the sulfide resin. Here, the alkali metal content of the polyphenylene sulfide prepolymer is, for example, a value calculated from the alkali metal in the ash that is a residue obtained by baking the polyphenylene sulfide prepolymer using an electric furnace or the like. It can be quantified by analyzing by a method or atomic absorption method.

  The alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium belonging to Group IA of the periodic table, but the polyarylene sulfide prepolymer of the embodiment of the present invention contains an alkali metal other than sodium. Preferably not.

  In addition, the polyphenylene sulfide prepolymer may be used with various catalyst components that promote the conversion upon conversion to a high degree of polymerization by heating. Examples of such catalyst components include ionic compounds and compounds having radical generating ability. Examples of ionic compounds include sulfur alkali metal salts such as sodium salt of thiophenol. Moreover, as a compound which has radical generating ability, the compound which generate | occur | produces a sulfur radical by heating can be illustrated, for example, The compound containing a disulfide bond can be illustrated more specifically. However, even in such a case, it is preferable that the alkali metal content, alkali metal species, and halogen species contained in the polyphenylene sulfide prepolymer conform to the above-described conditions. In addition, the reaction in which the polyphenylene sulfide prepolymer is heated to be converted into a high degree of polymerization is carried out with the amount of alkali metal in the reaction system being preferably less than 700 ppm by weight, more preferably 500 ppm or less, and even more preferably 300 ppm or less. And the disulfide weight based on the total sulfur weight in the reaction system is less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, still more preferably less than 0.1% by weight. It is desirable to do as. Preferably, this facilitates obtaining the (A ′) polyphenylene sulfide resin of the embodiment of the present invention. When various catalyst components are used, the catalyst component is usually taken into PAS, and the resulting PPS often contains the catalyst component. In particular, when an ionic compound containing an alkali metal and / or other metal component is used as a catalyst component, most of the metal component contained therein tends to remain in the obtained PPS. Moreover, PPS obtained using various catalyst components tends to increase the weight reduction rate when the PPS is heated. Therefore, when a higher purity PPS is desired and / or when a PPS with a low weight loss rate upon heating is desired, it is desirable to use as little as possible, preferably not, a catalyst component.

<Method for producing polyphenylene sulfide prepolymer>
Examples of the method for obtaining the polyphenylene sulfide prepolymer include the following methods.

  (1) By heating a mixture containing at least a polyhalogenated aromatic compound, a sulfidizing agent, and an organic polar solvent to polymerize a polyarylene sulfide resin, it is separated with an 80 mesh sieve (aperture 0.125 mm). A mixture containing a granular PPS resin, a PPS component produced by polymerization and other than the granular PPS resin (referred to as polyphenylene sulfide oligomer), an organic polar solvent, water, and an alkali metal halide salt is prepared. Thereafter, the polyphenylene sulfide oligomer contained in the mixture is separated and recovered and subjected to a purification operation to obtain a polyphenylene sulfide prepolymer.

  (2) A polyphenylene sulfide resin is polymerized by heating a mixture containing at least a polyhalogenated aromatic compound, a sulfidizing agent and an organic polar solvent. Then, after the polymerization is completed, the organic polar solvent is removed by a known method to prepare a mixture containing a polyphenylene sulfide resin, water, and an alkali metal halide, and the polyphenylene obtained by purifying the mixture by a known method A method of obtaining a polyphenylene sulfide resin containing a sulfide prepolymer and recovering the polyphenylene sulfide prepolymer by reprecipitating the obtained polyphenylene sulfide resin using a poor solvent.

<Conversion of polyphenylene sulfide prepolymer to a high degree of polymerization>
The (A ′) polyphenylene sulfide resin of the embodiment of the present invention described above is preferably produced by a method in which the polyphenylene sulfide prepolymer is heated to be converted into a high degree of polymerization. The heating temperature is preferably a temperature at which the polyphenylene sulfide prepolymer melts and is not particularly limited as long as such temperature conditions are satisfied. If the heating temperature is lower than the melting temperature of the polyphenylene sulfide prepolymer, a long time tends to be required to obtain a high degree of polymerization of PPS. The temperature at which the polyphenylene sulfide prepolymer melts varies depending on the composition and molecular weight of the polyphenylene sulfide prepolymer and the environment during heating, and cannot be uniquely indicated. For example, the polyphenylene sulfide prepolymer can be differentially scanned. It is possible to grasp the melting solution temperature by analyzing with a mold calorimeter. However, if the temperature at the time of heating is too high, it is representative of crosslinking reaction or decomposition reaction between polyphenylene sulfide prepolymers, between high polymerization degree PPS produced by heating, and between high polymerization degree PPS and polyphenylene sulfide prepolymer. The undesirable side reaction tends to occur, and the characteristics of the obtained PPS resin may be deteriorated. Therefore, it is desirable to avoid a temperature at which such an undesirable side reaction is remarkably generated. As heating temperature, 180 or more can be illustrated, Preferably it is 200 degreeC or more, More preferably, it is 250 degreeC or more. Moreover, as heating temperature, -400 degrees C or less can be illustrated, Preferably it is 200-380 degrees C or less, More preferably, it is 250-360 degrees C or less.

  Although the time for performing the heating differs depending on various characteristics such as cyclic polyphenylene sulfide content, m number, and molecular weight in the polyphenylene sulfide prepolymer to be used and conditions such as the heating temperature, it cannot be uniformly defined. It is preferable to set so that the aforementioned undesirable side reaction does not occur as much as possible. Examples of the heating time include 0.05 hours or more, preferably 0.1 hours or more. Moreover, as heating time, -100 hours or less can be illustrated, 0.1-20 hours or less are preferable and 0.1-10 hours or less are more preferable. When the heating time is less than 0.05 hours, the conversion of the polyphenylene sulfide prepolymer to the high polymerization degree PPS tends to be insufficient. In addition, when the heating time exceeds 100 hours, there is a tendency that an adverse effect on the characteristics of the PPS resin obtained by an undesirable side reaction tends to be manifested, and there is an economical disadvantage. There is.

  The conversion of the polyphenylene sulfide prepolymer to a high degree of polymerization by heating is usually performed in the absence of a solvent, but can also be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not substantially cause undesirable side reactions such as inhibition of conversion of the polyphenylene sulfide prepolymer to a high degree of polymerization by heating and decomposition or crosslinking of the produced high degree of polymerization PPS. As the solvent, for example, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide, sulfoxide / sulfone solvents such as dimethylsulfoxide and dimethylsulfone, acetone, methyl ethyl ketone, diethyl ketone, and acetophenone Ketone solvents such as dimethyl ether, dipropyl ether, and ether solvents such as tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, and Halogen solvents such as lorbenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol, and aromatic carbonization such as benzene, toluene, and xylene Examples thereof include hydrogen-based solvents. In addition, inorganic compounds such as carbon dioxide, nitrogen, and water can be used as a solvent in a supercritical fluid state. These solvents can be used as one kind or a mixture of two or more kinds.

  The conversion of the polyphenylene sulfide prepolymer to a high degree of polymerization by heating may be performed in a mold for producing a molded product, as well as by a method using a normal polymerization reaction apparatus, or by extrusion. Any apparatus equipped with a heating mechanism, such as a machine or a melt kneader, can be used without particular limitation, and a known method such as a batch system or a continuous system can be employed. The atmosphere during the conversion of the polyphenylene sulfide prepolymer to a high degree of polymerization by heating is preferably a non-oxidizing atmosphere, and preferably under reduced pressure. Moreover, when it carries out under pressure reduction conditions, it is preferable to make it the pressure reduction conditions after making the atmosphere in a reaction system once non-oxidizing atmosphere. This tends to suppress the occurrence of undesired side reactions such as cross-linking reactions and decomposition reactions between polyphenylene sulfide prepolymers, between high polymer PPS produced by heating, and between high polymer PPS and polyphenylene sulfide prepolymer. It is in. The non-oxidizing atmosphere refers to an atmosphere in which the oxygen concentration in the gas phase in contact with the polyphenylene sulfide prepolymer is 5% by volume or less, preferably 2% by volume or less, and more preferably substantially free of oxygen. The atmosphere containing substantially no oxygen refers to an inert gas atmosphere such as nitrogen, helium, or argon. Of these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling. The reduced pressure condition means that the pressure in the reaction system is lower than atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less. An example of the lower limit of the pressure in the system is 0.1 kPa or more. When the pressure under reduced pressure exceeds the preferable upper limit, an undesirable side reaction such as a crosslinking reaction tends to occur. On the other hand, when the pressure under reduced pressure is less than the preferred lower limit, the cyclic polyphenylene sulfide having a low molecular weight contained in the polyphenylene sulfide prepolymer tends to be volatilized depending on the reaction temperature.

(B) Mica The PPS resin composition of the present invention contains mica having a linseed oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less. When the linseed oil absorption amount of mica is less than 67 ml / 100 g, the effect of improving the interfacial adhesion between the PPS resin and the filler is not sufficiently obtained, resulting in a poor mechanical strength improving effect. As a result, with respect to 100 parts by weight of the PPS resin Therefore, a large amount of mica exceeding 30 parts by weight must be blended. In this case, the fluidity is lowered, and the surface smoothness of the resulting molded product is also impaired.

  On the other hand, if the linseed oil absorption amount of mica exceeds 90 ml / 100 g, mica breakage tends to occur during melt-kneading, the original filler reinforcing effect is not exhibited, and the mechanical strength is hardly improved, which is not preferable.

  In order not to sacrifice the fluidity, in order to maximize the reinforcing effect by improving filler adhesion with a small amount of mica, the linseed oil absorption amount of mica needs to be 67 ml / 100 g or more and 90 ml / 100 g or less. 70 ml / 100 g or more and 87 ml / 100 g or less is preferable, and 75 ml / 100 g or more and 80 ml / 100 g or less can be exemplified as a more preferable range.

  Here, the amount of linseed oil absorption of mica means a value measured according to JISK5101-13-2. Specifically, a mica sample and linseed oil are mixed in small amounts, and spirally wound using a spatula. The amount of linseed oil used per 100 g of sample when it is ready to be calculated.

  In addition, the linseed oil absorption amount of (B) mica used in the present invention is closely related to the mica structure, and when the oil absorption amount increases, the mica porosity improves and the PPS resin enters the mica and adheres to the filler by an anchor effect. On the other hand, since mica breakage easily occurs during melt kneading and the filler reinforcement effect is reduced at the same time, (B) mica oil absorption control used in the present invention maximizes the adhesion to the filler and the filler reinforcement effect. It is speculated that it was demonstrated.

  In the PPS resin composition of the present invention, the content of mica having an oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less is 1 to 30 parts by weight with respect to 100 parts by weight of the PPS resin. If the mica content is less than 1 part by weight, the mechanical strength is not sufficiently improved. On the other hand, when the content of mica exceeds 30 parts by weight, the fluidity and surface smoothness are remarkably lowered and the material specific gravity is increased, which is not preferable.

  In order to satisfy high fluidity, high dimensional stability, and high strength, the mica content is preferably 27 parts by weight or less, more preferably 25 parts by weight or less, and even more preferably 20 parts by weight or less.

  The volume average particle diameter of the mica used in the present invention is preferably 5 μm or more and 10 μm or less, and more preferably 7 μm or more and 9 μm or less from the viewpoint of not impairing the filler reinforcing effect and surface smoothness. When the volume average particle diameter of mica is larger than 10 μm, the oil absorption amount of (B) mica used in the present invention is less than 67 ml / 100 g, which is not preferable because the effect of increasing the strength by improving the original filler adhesion is not exhibited. On the other hand, if the volume average particle diameter of mica is smaller than 5 μm, the filler reinforcing effect is greatly reduced, which is not preferable.

  The volume average particle diameter of mica here is obtained by weighing 100 mg of mica, dispersing it in water, and using a laser diffraction / scattering particle size distribution measuring apparatus (LA-300 manufactured by HORIBA).

  (B) Mica used in the present invention can be further improved in mechanical strength by increasing the aspect ratio in addition to the linseed oil absorption and volume average particle diameter. ing. The aspect ratio here refers to a value calculated from volume average particle diameter (μm) / number average thickness (μm) by determining the volume average particle diameter and number average thickness of mica. The volume average particle size is obtained by weighing 100 mg of mica, dispersing it in water, and using a laser diffraction / scattering particle size distribution measuring device (LA-300 manufactured by HORIBA). The number average thickness was determined by measuring 10 thicknesses randomly selected from images of mica observed at a magnification of 2000 using a scanning electron microscope (SEM) (JSM-6360LV manufactured by JEOL Ltd.). The number average value is obtained.

  Mica having a linseed oil absorption of 67 ml / 100 g or more and 90 ml / 100 g or less used in the present invention is a naturally produced biotite, biotite, phlogopite, sericite, artificially produced synthetic mica. Either is acceptable. Two or more of these may be included.

  Examples of the mica production method include water jet pulverization, wet pulverization such as wet milling with a stone mill, dry ball mill pulverization, pressure roller mill pulverization, air flow jet mill pulverization, and dry pulverization using an impact pulverizer such as an atomizer. Etc.

  In the present invention, the surface of mica may be treated with a silane coupling agent or the like for the purpose of further improving the adhesion between mica and the PPS resin. Alternatively, mica that has been heat-treated for the purpose of removing impurities and hardening the mica may be used.

(C) An alkoxysilane compound having at least one group selected from an epoxy group, an amino group, and an isocyanate group In the present invention, for the purpose of further improving the adhesion between (A) PPS resin and (B) mica, (C) It is necessary to add a component as a filler adhesion improving aid.

  Specific examples of the alkoxysilane compound having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Examples include epoxy group-containing alkoxysilane compounds.

  Specific examples of the alkoxysilane compound having an amino group include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. Examples include amino group-containing alkoxysilane compounds.

  Specific examples of the alkoxysilane compound having an isocyanate group include γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatepropyl. Examples thereof include ethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane.

  Among them, an alkoxysilane compound containing an epoxy group is preferable and an alkoxysilane compound containing an isocyanate group is more preferable in order to maximize the effect of improving the adhesion between (A) PPS resin and (B) mica. preferable.

  The amount of component (C) is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the PPS resin. preferable. When the blending amount of the component (C) is less than 1 part by weight, it is difficult to obtain an effect of improving adhesion with a sufficient filler. On the other hand, in the range exceeding 30 parts by weight, the melt fluidity is significantly hindered and the material cost increases, which is not preferable.

(D) An ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol In the present invention, the component (D) is added for the purpose of improving moldability by imparting good releasability. It can be added as a release agent. In particular, the component (D) can balance low gas and good releasability at a high level, and has a property suitable as a release agent that hardly causes mold contamination.

  As the ester compound of component (D), an ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol is used. Examples of the aliphatic carboxylic acid having 12 to 40 carbon atoms include long-chain aliphatic carboxylic acids such as stearic acid, olefinic acid, pehenic acid, and montanic acid. Examples of the polyhydric alcohol include ethylene glycol, pentaerythritol, and polypentaerythritol. And polyhydric alcohols such as glycerin, trimethylolpropane and polytrimethylolpropane. It is preferable to use an ester compound obtained by reacting these, specifically, ethylene glycol distearate, pentaerythritol tetrastearate, polypentaerythritol polystearate, glycerin tristearate, trimethylolpropane tristearate, polytrislate. Examples thereof include methylol propane polystearate, ethylene glycol dimontanate, pentaerythritol tetramontanate, polypentaerythritol polymontanate, glycerin trimontanate, trimethylolpropane trimontanate, polytrimethylolpropane polymontanate, and the like.

  Component (D) is preferably added in an amount of 0.05 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the PPS resin. When the blending amount of the component (d) is less than 0.05 parts by weight, it is difficult to obtain a sufficient releasability improving effect. On the other hand, in the range exceeding 5 parts by weight, it is not preferable from the viewpoint of bleeding out to the surface of the molded product and an increase in gas generation amount.

(E) Fibrous filler The (E) fibrous filler in the present invention can be blended for the purpose of imparting high heat resistance and high dimensional stability. The (E) fibrous filler used in the present invention is defined as having a length / diameter ratio of 20 or more. Examples of (E) fibrous filler that can be used in the present invention include wollastonite, glass fiber, glass milled fiber, carbon fiber, metal fiber, carbon nanotube, and mineral fiber. Here, the preferred (E) fibrous filler for the present invention is a fiber having a fiber length of 1 to 5 mm before blending and a fiber diameter of 1 to 25 μm, generally referred to as a short fiber, and such a short fiber filler is used. Therefore, it tends to be easy to obtain a resin composition having good dispersibility of the filler. In addition, (E) the use of fibrous filler pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound is more excellent in mechanical strength. From the viewpoint of obtaining

  In the case of blending the (E) fibrous filler used in the present invention, the range of 50 parts by weight or less is selected with respect to 100 parts by weight of (A) polyphenylene sulfide, and the range of 1 to 30 parts by weight is more preferable. The range of 5 to 20 parts by weight is more preferable. (E) When the amount of the fibrous filler exceeds 30 parts by weight, the surface smoothness is lowered and excellent melt fluidity is not exhibited, which is not preferable.

Other Inorganic Fillers The PPS resin composition of the present invention can be used by further blending an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of such inorganic fillers include silicates such as fullerene, talc, zeolite, sericite, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, zirconium oxide, oxidation Metal compounds such as titanium and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads Non-fibrous fillers such as glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, carbon black and silica, and graphite are used. Of these, silica, calcium carbonate and talc are preferred, and calcium carbonate and talc are also preferred. , From the viewpoint of both the balance of surface smoothness and mechanical properties of the resin molded article. These inorganic fillers may be hollow, and two or more kinds may be used in combination. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

  The blending amount of the inorganic filler is preferably in the range of 1 to 50 parts by weight, more preferably in the range of 2 to 30 parts by weight, and further in the range of 5 to 20 parts by weight with respect to 100 parts by weight of the (A) PPS resin. preferable.

Other Additives Furthermore, in the PPS resin composition of the present invention, a resin other than (A) PPS resin may be added and blended within a range not impairing the effects of the present invention. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, tetrafluoropolyethylene resins, and olefin polymers and copolymers that do not contain an epoxy group such as ethylene / 1-butene copolymer.

  Moreover, the following compounds can be added for the purpose of modification. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds, polyetheretherketone, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, (3,9-bis [2- (3- (3 Phenolic compounds such as -t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) Such as antioxidants, (bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite) Phosphorus-based antioxidants, and other, water, lubricants, ultraviolet inhibitors, colorants may be blended with conventional additives such as foaming agents. If any of the above compounds exceeds 20% by weight of the total composition, (A) the original properties of the PPS resin are impaired, which is not preferable, and 10% by weight or less, more preferably 1% by weight or less is added.

Production Method of Resin Composition The PPS resin composition of the present invention is usually obtained by melt kneading. The melt-kneader is supplied to a generally known melt-kneader such as a single-screw, twin-screw extruder, Banbury mixer, kneader, and mixing roll, and kneaded at a melting peak temperature of the PPS resin + a processing temperature of 5 to 100 ° C. As a representative example, the method of performing can be cited. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended. Any method such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extruder may be used. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  Moreover, the composition of this invention can also employ | adopt the method of compressing and solidifying a compound to a tablet form in a solid state, and using this for shaping | molding, such as injection molding.

  The PPS resin composition obtained by the present invention is imparted with high fluidity, high dimensional stability, and high strength without impairing the original characteristics of the PPS resin, and the resulting molded product is excellent in surface smoothness and injection. Not only molding, injection compression molding, and blow molding, but also extrusion molding such as sheets, films, fibers, and pipes can be performed by extrusion molding.

As an application utilizing the moldability, high dimensional stability, and high strength of the PPS resin composition of the present invention,
For example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones , Small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electric and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair Dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark), audio / video equipment parts such as compact discs, digital video discs, lighting parts, refrigerator parts, Home parts such as computer parts, typewriter parts, word processor parts, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, Machine-related parts typified by typewriters, etc .: Optical equipment typified by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, water control valves, relief Water-related parts such as valves, hot water sensors, water sensors, water meter housings; valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel-related / exhaust systems, Various intake pipes, Air Take nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear Sensor, air conditioning thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle , Air conditioner panel switch board, coil for fuel related electromagnetic valve, hugh Connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, fuel tanks, ignition device cases, vehicle speed sensors, cable liners, etc.・ Vehicle related parts and other various uses can be illustrated.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

  In the following examples, material characteristics were evaluated by the following methods.

[Bar flow length]
Using an injection molding machine Promat 40/20 manufactured by Sumitomo Heavy Industries, Ltd. under the conditions of a resin temperature of 320 ° C., a mold temperature of 130 ° C., an injection speed setting of 99%, and an injection pressure setting of 45% (actual injection pressure of 98 MPa). , (Length) 150 mm × (width) 12.6 mm × (thickness) 0.5 mm (gate position: width side of molded piece, gate shape: film gate) were continuously injection-molded 10 times. Each of the obtained molded pieces was measured for the filling end length in the longitudinal direction from the gate position side, and the average value was taken as the rod flow length. It can be said that the greater the value of the rod flow length, the higher the fluidity.

[Injection molding of tensile specimen]
An ASTM No. 1 dumbbell test piece was molded under the conditions of a resin temperature of 320 ° C. and a mold temperature of 130 ° C. using an injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries.

[Tensile test]
The tensile strength and tensile elongation of the injection-molded ASTM No. 1 dumbbell test piece were measured according to ASTM D638 using a Tensilon UTA2.5T tensile tester under the conditions of a distance between fulcrums of 114 mm and a tensile speed of 10 mm / min. It can be said that the larger this value, the better the tensile properties.

[Injection molding of bending specimens]
Using the injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries, Ltd. under the conditions of a resin temperature of 320 ° C. and a mold temperature of 130 ° C., (width) 12.5 mm × (length) 130 mm × (thickness) 3.2 mm A bending test piece was formed.

[Bending test]
The injection-molded bending test piece was measured for bending strength and bending elastic modulus using a Tensilon RTM1T bending tester according to ASTM D790 under the conditions of a span distance of 100 mm and a crosshead speed of 1.0 mm / min. It can be said that the larger this value, the better the bending characteristics.

[Injection molding of impact test piece]
Using the injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries, under the conditions of a resin temperature of 320 ° C. and a mold temperature of 130 ° C., (width) 12.7 mm × (length) 60 mm × (thickness) 3.2 mm An Izod impact test piece with a mold notch was molded.

[Izod impact test]
Using the injection-molded notched Izod impact test piece, the notched Izod impact strength was measured according to ASTM D256. It can be said that the larger this value, the better the impact characteristics.

[Injection molding of surface smoothness evaluation plate]
(Length) 70 mm x (width) 70 mm x (thickness) 1.0 mm (gate shape: film) under the conditions of a resin temperature of 320 ° C. and a mold temperature of 150 ° C. using an injection molding machine SE75DUZ manufactured by Sumitomo Heavy Industries, Ltd. A plate having a gate and mold mirror surface roughness of 0.03 s was formed.

[Surface smoothness]
The injection molding surface smoothness evaluation plate (gate shape: film gate) was scanned by 2 cm in the resin flow direction (gate portion → filling end portion) using a surface roughness measuring instrument manufactured by Mitutoyo Corporation. Then, the centerline average roughness Ra defined in JISB0601 was measured, and an average value of n = 3 was adopted. In addition, it can be said that it is excellent in surface smoothness, so that this value is small.

(Material specific gravity)
The injection molded surface smoothness evaluation plate (gate shape: film gate, mold mirror surface roughness: 0.03 s) is cut into a size of (length) 30 mm × (width) 10 mm, and manufactured by Mirage Electronics Specific gravity was measured by a water displacement method using a hydrometer ED-120T.

[Mold shrinkage]
The amount of change of the injection-molded surface smoothness evaluation plate (film gate, mold mirror surface roughness: 0.03 s) with respect to the mold size in the flow direction (MD direction) and perpendicular direction (TD direction) is measured with a caliper. The molding shrinkage was calculated, and an average value of n = 3 was adopted. In addition, it can be said that it is excellent in dimensional stability, so that this value is small.

[Measurement of heat loss of PPS resin composition]
PPS resin composition pellets obtained by melt-kneading the blend and drying at 120 ° C. for 8 hours in the air were pre-dried at 130 ° C. for 3 hours, and about 10 g was precisely weighed in an aluminum cup. The loss on heating when this was treated at 320 ° C. for 2 hours in the atmosphere was measured. It can be said that the smaller the loss on heating, the smaller the amount of gas generated.

[Injection molding of IR reflow test piece]
Using the injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries, under the conditions of a resin temperature of 320 ° C. and a mold temperature of 130 ° C., (width) 12.6 mm × (length) 130 mm × (thickness) 1.5 mm An IR reflow test piece was molded.

[Surface mount IR reflow test]
The injection-molded IR reflow test piece was set in an IR reflow simulator device simulating a soldering surface mounting process for electronic components, and an IR reflow test was performed according to the temperature profile shown in FIG. Then, the amount of dimensional change before and after the reflow test of the test piece was measured at n = 2 as the amount of warp deformation. It can be said that the smaller this numerical value, the smaller the dimensional change at high temperature, and the better the IR reflow resistance.

[Evaluation of releasability]
As an index of releasability, a resistance force (release force) at the time of release was measured. As a specific method for measuring the mold release force, a mold having a molded product shape shown in FIGS. 1 and 2 is used, and an injection molding machine SE75DUZ manufactured by Sumitomo Heavy Industries, Ltd. is used. The mold release force was measured at a temperature of 150 ° C. and compared. To measure the mold release force, insert “Load Cell 1C-1B” manufactured by Technoplus into the mold, “MD-1031” manufactured by Toyo Paul Dwin for the strain amplifier, and “Memory High” manufactured by Hioki Denki. Using a coder 8840 ", the mold release force when the bottom surface of the molded product of FIG. 1 was projected with four ejector pins of φ10 was measured. The injection time was 10 seconds and the cooling time was 10 seconds. It can be said that when the value of the release force is low, the release property is excellent.

[Metal corrosion test]
PPS resin composition pellets obtained by melt-kneading the blend and drying at 120 ° C. for 8 hours in the air were pre-dried at 130 ° C. for 3 hours, and about 10 g was precisely weighed in an aluminum cup. Next, the glass plate was allowed to stand on the pellet, and a copper plate was placed on the plate. Finally, a petri dish was placed on the upper part of the aluminum cup to prepare for the metal corrosion test. After heat-treating a metal corrosion test sample in a hot air oven at 300 ° C. for 30 minutes. After the copper plate is taken out from the aluminum cup, the center line average roughness Ra of the copper plate surface is measured according to JISB0601, using a surface roughness measuring instrument manufactured by Mitutoyo Corporation, and an average value of n = 3 is obtained. Adopted. The copper plate surface Ra change rate was calculated from the copper plate surface Ra before and after the heat treatment, and the metal corrosivity was evaluated. In addition, it can be said that the smaller the rate of change, the more the metal surface roughness due to corrosion is suppressed, and the higher the corrosion resistance.

[Evaluation of dirt on molds]
As shown in FIG. 4, the size of the molded product has a maximum length of 55 mm, a width of 20 mm and a thickness of 2 mm. With a mold for use, using Sumitomo Heavy Industries' injection molding machine SE75DUZ, the cylinder temperature is 330 ° C., the mold temperature is 150 ° C., the injection speed is 100 mm / s, and the filling time for each resin composition is 0.4 seconds. The injection pressure is set within 50 to 80 MPa, continuous molding is performed with a holding pressure of 25 MPa, a holding pressure speed of 30 mm / s, and a holding time of 3 seconds until the mold contamination is visually confirmed in the gas vent and cavity. did. If the number of continuous shots in which mold contamination is visually confirmed is large, it can be said that the mold contamination is excellent.

[Evaluation of melt retention stability]
PPS resin composition pellets obtained by melt-kneading the blend and drying at 120 ° C. for 8 hours in the air were pre-dried at 130 ° C. for 3 hours, and then approximately 15 g was precisely weighed in an aluminum cup. Next, using the precisely weighed pellets, a melt residence time of 5 minutes and 30 minutes in a Capillograph manufactured by Toyo Seiki Co., Ltd. (orifice L / D = 10 mm / 1 mm, measurement temperature 300 ° C., shear rate 1000 / s, in an oxygen atmosphere) The melt viscosity (Pa · s) of was measured. And the melt viscosity change rate defined by the following mathematical formula was calculated. In addition, it can be said that it is excellent in melt residence stability, so that the value of a change rate of melt viscosity is small.
Melt viscosity change rate (%) = 100 (ηa / ηb-1)
Here, ηa in the above formula represents the initial melt viscosity with a melt residence time of 5 minutes, and ηb represents the melt viscosity after the melt residence with a melt residence time of 30 minutes.

[Reference Example 1] (A) Polymerization of PPS resin (A-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 861.00 g (10.5 mol), and ion-exchanged water 10500 g, and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS resin A-1 had a melt viscosity of 60 Pa · s (300 ° C., shear rate 1000 / s).

[Reference Example 2] (A) Polymerization of PPS resin (A-2)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS resin A-2 had a melt viscosity of 200 Pa · s (300 ° C., shear rate of 1000 / s).

[Reference Example 3] (A) Polymerization of PPS resin (A-3)
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and 10.5 kg of ion-exchanged water were charged, and the temperature was increased to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. After gradually heating and distilling out 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Thereafter, the mixture was cooled to 200 ° C., 10.45 kg (71.07 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. .

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

  The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS (a-3). The obtained PPS resin A-3 had a melt viscosity of 140 Pa · s (300 ° C., shear rate of 1000 / s).

Reference Example 4 (A ′) Polymerization of PPS resin (A′-1)
1.648 kg of sodium hydrosulfide 48 wt% aqueous solution (0.791 kg (14.1 mol) of sodium hydrosulfide), 48 wt% aqueous solution of sodium hydroxide in a 1 liter autoclave equipped with a stirrer and an extraction valve at the top 1.225 kg (0.588 kg (14.7 mol) of sodium hydroxide), 35 L of N-methyl-2-pyrrolidone (NMP), 2.120 kg (14.4 mol) of p-dichlorobenzene (p-DCB) Prepared.

  The reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, and then heated from room temperature to 200 ° C. over 25 minutes while stirring at 400 rpm. Next, the temperature was raised to 250 ° C. over 35 minutes, and the reaction was performed at 250 ° C. for 2 hours. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 26.6 kg of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature and the contents were collected.

  The collected contents were heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a stainless steel mesh with an average opening of 10 μm, and the obtained filtrate component was dropped into about three times the amount of methanol to recover the precipitated component. The obtained solid component was reslurried with about 2.5 L of 80 ° C. warm water, stirred for 30 minutes at 80 ° C. and then filtered three times, and then the obtained solid content was dried at 80 ° C. under reduced pressure for 8 hours. To obtain a dry solid. As a result of analysis by infrared absorption spectrum and high performance liquid chromatography of the obtained dried solid, it was found that it contained 85% by weight of cyclic polyphenylene sulfide.

  The obtained dried solid was charged into a glass test tube equipped with a distilling tube and a stirring blade, and then reduced pressure and nitrogen substitution in the test tube were repeated three times. While maintaining the inside of the test tube at about 0.1 kPa, the temperature was adjusted to 340 ° C. and heated for 120 minutes, and then cooled to room temperature to obtain a polymer. The product obtained from the infrared spectroscopic spectrum of the product was polyphenylene sulfide, and GPC measurement showed that the weight average molecular weight was about 50,000 and the degree of dispersion was 2.35. Further, the obtained PPS resin A′-1 had a melt viscosity of 70 Pa · s (300 ° C., shear rate 1000 / s).

[Reference Example 5] (B) Mica (B-1) Mica, volume average particle diameter: 7 μm, number average thickness 0.06 μm
Aspect ratio 110, Linseed oil absorption 70ml / 100g
(B-2) Mica, volume average particle diameter: 5 μm, number average thickness 0.05 μm
Aspect ratio 100, Linseed oil absorption 80ml / 100g
(B-3) Mica, volume average particle diameter: 3 μm, number average thickness 0.05 μm
Aspect ratio 60, Linseed oil absorption 95ml / 100g
(B-4) Mica, volume average particle diameter: 20 μm, number average thickness 0.25 μm
Aspect ratio 80, Linseed oil absorption 60ml / 100g
(B-5) Mica, volume average particle diameter: 40 μm, number average thickness 0.50 μm
Aspect ratio 80, Linseed oil absorption 40ml / 100g
(B-6) Mica, volume average particle diameter: 8 μm, number average thickness: 0.045 μm,
Aspect ratio: 177, Linseed oil supply amount: 60ml / 100g

  The volume average particle size was determined by LA-300 manufactured by HORIBA, a laser diffraction / scattering particle size distribution measuring apparatus. The thickness was observed at a magnification of 2000 using a scanning electron microscope (SEM) (JSM-6360LV manufactured by JEOL Ltd.). Ten mica particles were randomly selected from the image, the thickness was measured, and the number average value was obtained. The aspect ratio was calculated as volume average particle diameter (μm) / number average thickness (μm). Linseed oil absorption was measured according to JISK5101-13-2 measuring method (established on February 20, 2004).

[Reference Example 6] (C) an alkoxysilane compound (C-1) having at least one group selected from an epoxy group, an amino group and an isocyanate group (C-1) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu) Chemical Industry KBM-303)
(C-2) 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.).

[Reference Example 7] (D) An ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms and a polyhydric alcohol (D-1) pentaerythritol tetrastearate (Roxyol VPG861 manufactured by Emery Ole Chemicals Co., Ltd.) .

[Reference Example 8] Compound other than Reference Example 7 (D′-1) Amide wax composed of stearic acid, sebacic acid and ethylenediamine (Kyoeisha Chemical Co., Ltd. Light Amide WH-255)
(D′-2) Polyethylene wax (Lycowax PE190 manufactured by Clariant Japan Co., Ltd.).

[Reference Example 9] (E) Fibrous filler (E-1) wollastonite (NYAD1250, Sakai Kogyo Co., Ltd., number average fiber diameter 3 μm, number average fiber length 9 μm, aspect ratio 3)
(E-2) Wollastonite (manufactured by Sakai Kogyo Co., Ltd. NYGLOS4W, number average fiber diameter 4.5 μm, number average fiber length 50 μm, aspect ratio 11)
(E-3) Glass fiber (Nippon Electric Sheet Glass Co., Ltd. milled fiber EPG70M-01N, number average fiber diameter 9 μm, number average fiber length 70 μm, aspect ratio 8)

[Examples 1-14, Comparative Examples 1-4]
After the components shown in Tables 1 and 2 were dry blended at the ratios shown in Tables 1 and 2, a TEX30α twin screw extruder (screw diameter 30 mm, L / D) manufactured by Nippon Steel Works, equipped with a vacuum vent. = 45, 5 kneading sections, fully meshing screw rotating in the same direction), and setting the cylinder temperature so that the resin temperature at which the die is discharged is 310 ° C. at a screw speed of 300 rpm and a discharge rate of 20 kg / hr. The mixture was melt kneaded and pelletized with a strand cutter. Pellets dried overnight at 130 ° C are subjected to injection molding, material specific gravity, rod flow length, mechanical properties, dimensional stability, surface smoothness, mold release, IR reflow resistance, mold stain resistance, corrosion resistance, The melt residence stability was evaluated. The results were as shown in Tables 1 and 2.

  The results of Examples 1-14 and Comparative Examples 1-4 will be compared and described.

  Examples 1 and 5 in which mica oil absorption is in the range of 67 ml / 100 g or more and 90 ml / 100 g or less are blended with (B-1) and (B-2) mica in (A-1) PPS resin. (B-3), (B-4), (B-5), and (B-6) deviating from the range of the mica oil absorption used in the comparison with Comparative Examples 1 to 4 using mica, It was the result of increasing the strength by improving the adhesion between the resin and the filler without impairing fluidity and dimensional stability.

  Example 2 and Example 6 in which (C-1) an alkoxysilane compound was blended with respect to Example 1 and Example 5 were compared with Examples 1 and 5 in which (C) component was not blended. As a result, the adhesion between the mica and the mica was improved, and the mechanical strength was further improved. Example 3 in which the (A-1) PPS resin used in Example 1 was changed from the (A-1) PPS resin to the (A-2) PPS resin resulted in higher strength than Example 1 due to improved toughness. Obtained. In contrast to Example 2, Example 4 in which the (C) alkoxysilane compound was changed from (C-1) to (C-2) resulted in a further improvement in mechanical strength, although fluidity was slightly reduced. It was.

  Compared with Example 7-9 which mix | blended (D-1) ester compound and the other (D'-1) and (D'-2) component with respect to Example 1, mechanical property and surface smoothness In all cases, the release properties were improved without impairing the properties. Especially Example 7 which mix | blended (D-1) was the result of having a 320 degreeC gas generation amount small compared with Examples 8 and 9, and being extremely excellent in mold | die stain | pollution | contamination property.

  Compared to Example 1, Example 10 in which (A-1) PPS resin is changed to (A-3) PPS resin has a mold release force in the shape shown in FIGS. In addition, a result that the releasability was further improved was obtained. Further, Example 11 in which (A-1) PPS resin is changed to (A′-1) PPS resin with respect to Example 1 can significantly reduce the gas compared to Example 1 and can be releasable. Further, the results were obtained that IR reflow resistance, melt residence stability, and corrosion resistance were remarkably improved.

  In contrast to Example 1, (B-1) Examples 12 to 14 in which (E-1), (E-2), and (E-3) fibrous filler are used in combination with mica are synergistic with fibrous filler reinforcement. Due to the effect, a result that IR reflow resistance was further improved without significantly deteriorating other characteristics was obtained.

  G Gate

Claims (6)

(A) The linseed oil absorption (based on JISK5101-13-3 (2004)) is 67 ml / 100 g or more and 90 ml / 100 g or less with respect to 100 parts by weight of the polyphenylene sulfide resin (B) 1-30 parts by weight of mica A polyphenylene sulfide resin composition comprising: (A) 1 to 30 parts by weight of an alkoxysilane compound having at least one group selected from an epoxy group, an amino group and an isocyanate group is blended with 100 parts by weight of polyphenylene sulfide. The polyphenylene sulfide resin composition according to claim 1. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the volume average particle diameter of the (B) mica is 5 μm or more and 10 μm or less. (A) 0.05 to 5 parts by weight of an ester compound obtained by reacting (D) an aliphatic carboxylic acid having 12 to 40 carbon atoms and a polyhydric alcohol with respect to 100 parts by weight of the polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to any one of claims 1 to 3. 5. The polyphenylene sulfide resin composition according to claim 1, wherein 1 to 50 parts by weight of (E) fibrous filler is contained with respect to 100 parts by weight of (A) polyphenylene sulfide. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 5.