JP5428391B2 - Method for producing polyarylene sulfide resin composition in which metal element-containing nanoparticles are dispersed - Google Patents

Description

  The present invention relates to a method for producing a polyarylene sulfide resin composition in which metal element-containing nanoparticles are dispersed.

  Polyarylene sulfide resin (hereinafter abbreviated as PAS resin) has excellent heat resistance, chemical resistance, flame resistance, rigidity, and mechanical properties. As so-called engineering plastics, electrical and electronic parts, automobile parts, machinery Widely used in parts and structural parts. While the PAS resin has these excellent properties, it has a defect that it is brittle with poor toughness, especially ductility, and there are examples in which various inorganic fillers such as glass fibers are added as reinforcing agents in order to compensate for this. Many. However, since these inorganic fillers are usually on the order of μm and the contact area with the matrix resin is not large, it is necessary to add a large amount of 30 to 50% by mass in order to improve brittleness. On the other hand, there is a method of directly melt-kneading nano-sized inorganic filler so that a large amount of filler does not need to be added. Secondary aggregation cannot be dispersed. Therefore, there has been a problem that the effect of using the nanofiller is not sufficiently exhibited. In order to obtain a better filler dispersion state during melt kneading, it is generally necessary to apply a strong shearing force. In this case, there is a risk of deterioration of PAS due to shearing heat generation or air oxidation, abnormal cross-linking or main chain breakage, and there is a problem that the melt kneading temperature, shear rate, etc. must be controlled.

  In contrast, by dissolving inorganic metal salts (metal chloride, sulfide, etc.) in a solvent capable of these, mixing this solution with PAS resin, removing the solvent, and melt-kneading the obtained material. A manufacturing method for a composite of a PAS resin obtained by reducing a metal in a metal compound and a single metal is disclosed (for example, see Patent Document 1). According to this method, the PAS resin is composed of 95 to 99.99% by weight and at least one metal selected from Group VIII and Group Ib of 0.01 to 5% by weight, and the metal is averaged in the PAS matrix. A composite having a particle size of 0.5 to 30 nm and uniformly dispersed is obtained.

However, in the method described in Patent Document 1, a metal salt is dissolved in a solvent for the purpose of dispersing the metal raw material. However, in order to perform melt kneading smoothly, it is necessary to remove the solvent before melt kneading. PAS resin does not dissolve in various solvents at room temperature. Therefore, the metal salt dissolved with the present solvent removal operation again aggregates on the PAS resin surface as before the dissolution. Therefore, the effect of the solvent dissolution-solvent removal operation on the additive raw material for good metal dispersion is limited, and when the entire composite material is observed in detail, coarse particles may remain even after melt-kneading.
In addition, since the melt-kneading step is substantially performed, the above-described problem relating to melt-kneading has not been solved.

JP-A-8-208849

  An object of the present invention is to provide a method for producing a PAS resin composition in which metal element-containing nanoparticles are dispersed without performing melt kneading.

The present inventor disperses the PAS resin and the inorganic metal compound in an organic solvent capable of dissolving the PAS resin, and then deposits the metal element-containing nanoparticles easily without melting and kneading. It was found that a PAS resin composition was obtained.
Since both the PAS resin and the inorganic metal compound are dissolved in the organic solvent at one end, and both are precipitated almost simultaneously, a composition in which the metal element-containing nanoparticles derived from the inorganic metal compound are uniformly dispersed in the PAS resin is obtained. Can do.
In this method, since the inorganic metal compound is once dissolved and reprecipitated, the obtained metal element-containing particles are easily nanosized. Furthermore, when the metal in the inorganic metal compound is of a type that can be easily reduced (noble metal type), it can be expected that a dispersion of single metal nanoparticles can be expected or reduced to a PAS resin during a process such as dissolution and precipitation. When the compound is deposited as it is, a dispersion of inorganic metal compound nanoparticles can be expected.
Furthermore, since the PAS resin used as the matrix is dissolved in the solvent and the polyarylene sulfide molecular chain is expanded more than during melt kneading, the precipitated metal element-containing nanoparticles are more easily dispersed uniformly. Therefore, it is possible to obtain a PAS resin composition in which metal element-containing particles having an extremely small particle size are dispersed.

  That is, the present invention relates to a PAS resin composition in which metal element-containing nanoparticles are dispersed, wherein the PAS resin and the inorganic metal compound are dissolved in an organic solvent capable of dissolving the PAS resin and then precipitated. A manufacturing method is provided.

According to the present invention, a PAS resin composition in which metal element-containing nanoparticles are dispersed can be produced without performing melt kneading. Since melt kneading is not performed, there is no shearing force applied to the PAS resin during melt kneading, and there is no risk of oxidative deterioration of the resin or main chain breakage.
In addition, since the PAS resin as a matrix is used as a solvent, the metal element-containing nanoparticles precipitated between the polyarylene sulfide molecular chains expanded than during melt kneading are more easily dispersed and do not include coarse particles on the order of micrometers. It is possible to obtain a PAS resin composition in which metal element-containing particles having an extremely small particle size are dispersed.

(Definition of words “metal element-containing nanoparticles”)
The “metal element-containing nanoparticles” contained in the composition obtained by the production method of the present invention are nanoparticles of metal element-containing compounds. This is a particle obtained by dissolving and reprecipitating the metal compound to be used, which will be described later, in an organic solvent together with the PAS resin. Depending on the metal species of the metal compound to be used and the conditions for dissolution and precipitation, the precipitated particles are dissolved. In addition to the previous metal compound itself, it is presumed to include a metal ion species, a reduced metal simple substance, and a metal oxide oxidized by a coexisting component (residual moisture, oxygen derived from the raw metal compound). In the present invention, since it was proved that the nanoparticles contained in the obtained composition contain a metal element, such an expression is used.

(PAS resin)
The PAS resin used in the present invention is not particularly limited, and a known PAS resin can be used. Examples thereof include a random copolymer containing a repeating unit having a structure in which an aromatic ring which may have a substituent and a sulfur atom are bonded, a block copolymer, a mixture thereof or a mixture with a homopolymer.
Typical examples of these PAS resins include polyphenylene sulfide (hereinafter referred to as PPS resin). Among the PPS resins, those having a structure in which the bond of the repeating unit to the aromatic ring is in the para position are preferable in terms of heat resistance and crystallinity.

(Bonded species)
The PAS resin has a meta bond, an ether bond, a sulfone bond, a sulfide ketone bond, a biphenyl bond, a phenyl sulfide bond, and a naphthyl bond with an upper limit of less than 10 mol% (however, a component containing a tri- or higher functional bond is copolymerized). When it is made to be contained, the upper limit may be 5 mol%). In the present invention, as described later, it is considered that sulfide (-S-) contributes to the dispersion of the metal-containing material. Therefore, it is not suitable to use a PAS resin whose density is greatly reduced by copolymerization.

(Molecular weight)
Although there is no restriction | limiting in particular about the molecular weight distribution of PAS resin used for this invention, It is preferable that it is below a fixed molecular weight from a viewpoint that the melt | dissolution to the solvent of polyphenylene sulfide in the case of composite operation is easy. Preferably, the peak molecular weight of the molecular weight distribution determined by gel permeation chromatography using 1-chloronaphthalene as a solvent is 50,000 or less, more preferably 45,000 or less.

  In addition, the peak molecular weight in this invention is based on the numerical value calculated | required as a polystyrene conversion amount, using polystyrene as a standard substance in the gel permeation chromatograph measurement of a postscript Example. While the number average molecular weight and mass average molecular weight change depending on how the baseline of the molecular weight distribution curve of gel permeation chromatography is taken, the peak molecular weight depends on how the baseline of the molecular weight distribution curve is taken. Is not.

The melt viscosity of the PAS resin used in the present invention is not particularly limited as long as the viscosity at 300 ° C. and a shear rate of 500 sec ⁻¹ is 20 to 1000 Pa · s as measured using a cavity rheometer.

(Method for producing PAS resin)
The method for producing the PAS resin is not particularly limited. For example, 1) a method in which a dihalogenoaromatic compound and, if necessary, another copolymerization monomer are polymerized in the presence of sulfur and sodium carbonate, and 2) a dihalogenoaromatic. A method of polymerizing a group compound and, if necessary, other copolymerization monomers in the presence of a sulfidizing agent in a polar solvent, 3) p-chlorothiophenol, and, if necessary, other copolymerizations Examples thereof include a method of self-condensing a monomer and 4) a method of reacting a sulfidizing agent, a dihalogenoaromatic compound, and, if necessary, another copolymerization monomer in an organic polar solvent.
Among these methods, the method 4) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization.
Among the above methods 4), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound and A method for producing a PAS resin by reacting with a sulfidizing agent and controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent (See JP-A No. 07-228699).

(Organic solvent)
In the present invention, since it is essential that the PAS resin is dissolved in an organic solvent, the organic solvent to be used needs to be able to dissolve the PAS resin under a certain condition. The conditions for dissolving the PAS resin may be normal temperature or under heating, but in a currently known solvent, heating to a certain temperature is necessary in order to dissolve the PAS resin having a certain molecular weight or more. As a solvent capable of dissolving the PAS resin, N-methyl-2-pyrrolidone (NMP), hexamethylphosphoric triamide, N-cyclohexylpyrrolidone, N-methylcaprolactam, tetramethylurea, dimethylformamide, Examples thereof include dimethylacetamide, tetramethylene sulfoxide, dimethyl sulfoxide, and the like as sulfoxide solvents, and polyethylene dialkyl ether, 1-chloronaphthalene, and diphenyl sulfide as other solvents. Among these, amide solvents are particularly preferably used because various inorganic metal compounds can be easily dissolved, the composite component can be widely selected, and the composite component content can be increased. Of these, NMP is particularly preferable.

(Inorganic metal compound)
The inorganic metal compound used in the present invention may be mostly dissolved in the organic solvent under the condition that the PAS resin is dissolved in the organic solvent (mainly under heating). Inorganic metal compounds that can be used are metal halides such as metal chloride, metal bromide, metal iodide, metal perchlorate, metal chlorate, metal nitrate, and oxyhalide, which are relatively soluble in organic solvents. It is preferable because it is high. Metal oxides, metal sulfates, metal sulfites, metal borates, metal phosphates, and metal sulfides can also be used as long as the materials other than these satisfy the conditions for dissolution in the organic solvent. These may be hydrates.

(Metal compound; metal species)
The metal species used in the organic or inorganic metal compound is not particularly limited, but typical metals and transition metals are preferably used. Typical metals are aluminum, zinc, indium, tin, lead, antimony, etc. Transition metals are titanium, zirconium, hafnium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, palladium, platinum Various metals such as copper, silver, gold, and cerium can be exemplified, but are not limited thereto. Moreover, you may use multiple types of these metal compounds as needed.

(Production method)
The PAS resin and the inorganic metal compound are dissolved in the organic solvent and then precipitated. PAS resin is said to be insoluble in various solvents at room temperature, and in order to dissolve the PAS resin, heating is substantially required. Specifically, an organic material that can dissolve the PAS resin at a high temperature is used. The PAS resin and the inorganic metal compound are dissolved in a solvent, and then cooled and precipitated. Therefore, as a manufacturing apparatus used for the manufacturing method of this invention, it is an apparatus with a dissolution tank which can dissolve a PAS resin and an inorganic metal compound in an organic solvent, and a heating facility is required. Furthermore, when the temperature required for heating is near the boiling point of the organic solvent to be used or exceeds the boiling point, a pressure resistant container is required to effectively perform the heating. An autoclave can be illustrated as a pressure-resistant container which can be heated. Usually, a PAS resin (especially PPS) synthesis facility can be preferably used because it includes a pressure-resistant container that can be heated.
As another method, the PAS resin solution may be poured into a poor solvent such as water or alcohol and precipitated.

The resin deposited by the production method of the present invention is a PAS resin before dissolution, but the nanoparticles may have different structures depending on the type of inorganic metal compound used and dissolution deposition conditions as described above.
The structure of the nanoparticles in the present invention or the complexed state with the PAS resin has not been fully clarified, but the following four types of states are presumed.
(1) Single metal: It is known that the PAS resin oxidizes sulfide sites with sulfoxide and sulfone, and oxidizes benzene ring sites at high temperatures. Therefore, it has the ability to reduce the coexisting inorganic metal compound. When the metal in the inorganic metal compound used as the raw material for the composite is of a type that can be easily reduced (noble metal), it may be composited as a single metal.
(2) Metal oxide: When the metal in the inorganic metal compound used as a raw material is a base metal that is difficult to be reduced, it is not reduced by the PAS resin. In this case, since a metal oxide is generally the most stable as the metal compound, there is a possibility that it is oxidized by moisture contained in the PAS resin, the organic solvent, or oxygen contained in the inorganic metal compound.
(3) Metal ions: Since aromatic rings and sulfide sites, which are the basic components of PAS resins, have electron donating properties, metal ions may be able to be complexed in a coordinate bond. Assuming that the metal-containing material is trapped in the PAS molecular chain by electron donation from the sulfide site or aromatic ring of the PAS resin during dissolution and precipitation, the metal species can have a high oxidation number and a high coordination number. Is preferred.
(4) Inorganic metal compound: The stability of the inorganic metal compound used as a raw material is very high, and when it is not decomposed by solvent dissolution or heating, it may be combined as inorganic metal compound fine particles without changing from the raw material. .

  The composite state of the precipitated nanoparticles and the PAS resin is presumed that the PAS resin as the matrix is dissolved in the solvent and that the polyarylene sulfide molecular chain is expanded more than during melt kneading. It is estimated that the precipitated metal element-containing nanoparticles were more uniformly dispersed, and a PAS resin composition in which metal element-containing particles having an extremely small particle size were dispersed could be obtained.

(Average particle size of metal element-containing nanoparticles)
The average particle size of the metal element-containing nanoparticles in the composition obtained by the production method of the present invention is such that when the particle size of the fine particles is small, the particle surface area per particle mass increases, so that the addition effect can be exhibited with a small amount of addition. Therefore, the average particle size is preferably 1 μm or less, more preferably 500 nm or less, and most preferably 100 nm or less.
Examples of the method for measuring the average particle size of the metal element-containing nanoparticles include a method of calculating from observation results of a scanning electron microscope, a transmission electron microscope, etc., because it is necessary to directly observe the particle size in the resin composition. it can. In addition, the particle size distribution and shape of the metal element-containing nanoparticles are not particularly limited as long as they are designed so as to have an optimum shape depending on the application destination of the composition obtained in the present invention.

(Content of metal element-containing nanoparticles)
The content of the metal element-containing nanoparticles in the composition obtained by the production method of the present invention is not particularly limited. However, in this method, since it can be combined with an extremely small particle size, even when the content is lower than that of a normal melt-kneading method, for example, a content of 0.01% by mass or more, as a resin reinforcing material or modifier. The role of can be expressed. On the other hand, the upper limit of the content is preferably 0.01% by mass to 20% by mass because the fine particle size of the metal element-containing nanoparticles may not be maintained.

(High molecular weight PAS resin)
The PAS resin dissolution conditions generally coincide with the PAS resin synthesis conditions. Therefore, the properties of the PAS resin composition can be further improved by simultaneously performing an operation for increasing the molecular weight using the terminal functional group remaining in the PAS resin. This process is known as postcondensation. As a specific example, the halogen terminal remaining in the PAS resin synthesized using a dihalogenoaromatic compound as a raw material may be reacted with the inorganic metal compound simultaneously with the reaction of the remaining terminal with an appropriate amount of a sulfidizing agent. It can be illustrated. By this operation, the halogenation of the PAS resin can be promoted.

  In addition, by combining a PAS resin and an inorganic metal compound in combination with an inorganic material that is not dissolved in an organic solvent but is well dispersible, or an organic material that is soluble in an organic solvent, a third operation is performed. You may perform operation which adds a component.

(Purification operation of the composition)
As a purification operation of the obtained composition, an organic solvent and a by-product (for example, a thermal decomposition product of an inorganic metal compound) contained in the composition after the production of the composition can be removed. It is not limited. Examples of the method for removing the organic solvent include water washing, steam washing, solvent washing, distillation treatment, solvent removal by flash operation, and the like.

(Post-processing and combined materials)
The PAS resin composition in which the metal element-containing nanoparticles obtained by the present invention are dispersed may be processed directly into a desired shape using this as a material, and this may be further applied to a PAS resin or other thermoplastic resin. You may combine and use. Further, it may be used in combination with known and commonly used inorganic fillers and thermoplastic elastomers.

  Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto.

<Synthesis Example 1 Synthesis of PAS Resin (PPS-1)>
A titanium reaction vessel equipped with a stirring blade connected with a temperature sensor, cooling tower, dropping tank, dropping pump, distillate separation tank, paradichlorobenzene (p-DCB) 1838 kg (12.5 kgol), N-methyl-2-pyrrolidone (NMP) 4958 kg (50 kgol) and 90 kg (5.0 kgol) of water were charged at room temperature, and the temperature was raised to 100 ° C. over 20 minutes under stirring in a nitrogen atmosphere, the system was closed, and further to 220 ° C. for 40 minutes. The internal pressure was controlled at 0.22 MPa at that temperature, and a mixture of Na ₂ S · xH ₂ O 1500 kg, NaSH · yH ₂ O 225 kg, water 425 kg (Na ₂ S: 11.4 kgol, NaSH: 3.2 kgol, water 50.3 mass%) was added dropwise over 3 hours. During the dropping, dehydration was performed simultaneously, water was removed from the system, and p-DCB distilled together with water was continuously returned to the autoclave. The dehydration operation and the operation for returning the p-DCB were performed until the temperature increase at 240 ° C. was completed, and the system was sealed when the temperature increase was completed.

Then, after maintaining for 1 hour at the same temperature and pressure, the internal temperature was raised to 240 ° C. while reducing the internal pressure to 0.17 MPa over 1 hour, and the reaction was terminated by maintaining the temperature for 1 hour. Cooled to room temperature.
According to the analysis result of the distillate, the amount of water in the reaction system at the end of the reaction was 0.17 (mol / mol) with respect to the total sulfidizing agent used.
The obtained reaction slurry was heated to 120 ° C. under reduced pressure (−0.08 MPa), the reaction solvent was distilled off, water was poured into the residue, and the mixture was stirred at 80 ° C. for 1 hour, followed by filtration. The cake was stirred again with hot water for 1 hour, washed, and then filtered. This operation was repeated three times, water was further added, the mixture was stirred at 200 ° C. for 1 hour, filtered, and dried with a hot air dryer at 120 ° C. for 10 hours to obtain a white powdery polymer. This polymer is hereinafter referred to as PPS-1. The peak molecular weight of this PPS-1 was 43,700, and the melt viscosity was 240 Pa · s.

(Example 1: Manufacturing method of PAS resin composition in which metal element-containing nanoparticles are dispersed using copper (II) chloride dihydrate (hereinafter abbreviated as nanoparticle-dispersed PAS composition)
In a 2 L beaker, N-methyl-2-pyrrolidone (NMP) 800 g as an organic solvent and 10.0 g of copper chloride (II) chloride dihydrate as a metal chloride as an inorganic metal compound were charged and stirred at room temperature for 30 minutes. A dark green NMP solution was obtained by complete dissolution.
Prepared in Synthesis Example 1 as a PAS resin after putting the previously prepared NMP solution into a titanium reaction kettle with a stirring blade with an internal volume of 2 L connected to a temperature sensor and a nitrogen gas line (inlet and outlet 1 each) 200 g of the prepared PPS-1 was charged and completely sealed. Thereafter, the nitrogen gas inlet and outlet were opened, and the nitrogen gas was circulated at a flow rate of 1 L / min for 10 minutes to replace the air in the container, and then the nitrogen gas inlet and outlet were closed. While stirring the inside of the tank at a rotation speed of 300 min ^−1, the temperature was increased at 4 ° C./min, and after reaching 250 ° C., the temperature was maintained for 30 minutes.
Thereafter, the temperature in the tank was lowered at 4 ° C./min while maintaining stirring, and when the temperature reached 70 ° C., stirring was stopped and the kettle was opened. There was a uniform brown lump inside, and the two-phase product of the NMP solution and the resin before heating was completely different. The lump was placed in 2 L of ion-exchanged water and stirred at room temperature for 30 minutes for dispersion washing, and this dispersion slurry was poured onto 90 mmφ Nutsche from a Kiriyama funnel 5B filter paper and filtered under reduced pressure. The washing filtrate became transparent by repeating the operation of dispersing and washing the resin composition on the filter paper with 2 L of ion exchange water twice. The resin composition on the filter paper collected here was spread on a metal vat and dried with hot air at 120 ° C. for 14 hours to obtain a nanoparticle-dispersed PAS composition.

(Example 2: Production method of nanoparticle-dispersed PAS composition using iron (III) chloride)
Instead of the copper (II) chloride dihydrate used in Example 1, 20.0 g of iron (III) chloride was completely dissolved in NMP at room temperature, except that a brown NMP solution was used. The nanoparticle-dispersed PAS composition was obtained by performing the same composite, washing, and drying operations as in Example 1.

(Example 3: Method for producing nanoparticle-dispersed PAS composition using zirconium oxychloride octahydrate)
Instead of the copper (II) chloride dihydrate used in Example 1, a colorless and transparent NMP solution obtained by completely dissolving 10.0 g of zirconium oxychloride octahydrate in NMP at room temperature was used. A nanoparticle-dispersed PAS composition was obtained by performing the same composite, washing and drying operations as in Example 1 except for the above.

(Example 4: Production method of nanoparticle-dispersed PAS composition using nickel (II) bromide trihydrate)
Instead of the copper (II) chloride dihydrate used in Example 1, 5.0 g of nickel (II) bromide trihydrate was completely dissolved in NMP at room temperature to obtain a green NMP solution. A nanoparticle-dispersed PAS composition was obtained by performing the same compositing, washing, and drying operations as in Example 1 except that they were used.

(Example 5: Production method of nanoparticle-dispersed PAS composition using cobalt nitrate (II) hexahydrate)
Instead of the copper (II) chloride dihydrate used in Example 1, a blue NMP solution obtained by completely dissolving 3.0 g of cobalt (II) nitrate hexahydrate in NMP at room temperature was used. A nanoparticle-dispersed PAS composition was obtained by performing the same compositing, washing and drying operations as in Example 1 except for the above.

(Example 7: Method for producing nanoparticle-dispersed PAS composition using zinc iodide)
Instead of the copper (II) chloride dihydrate used in Example 1, 25.0 g of zinc iodide was completely dissolved in NMP at room temperature, except that a pale yellow NMP solution was used. The nanoparticle-dispersed PAS composition was obtained by performing the same composite, washing and drying operations as in Example 1.

(Comparative Example 1: Preparation of composite by melt kneading method, equivalent to comparison of Example 1)
A test for kneading a PAS resin and an inorganic metal compound by a melt kneading method under the following conditions using a resin melt kneading apparatus, Laboplast mill C type, KF-6 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) It was. This comparative example has a composition corresponding to the comparative test of Example 1. Introducing 5.0 g of dry blended PPS-1 resin powder and 0.25 g of copper (II) chloride dihydrate powder while rotating the kneading blade at a mixer rotation speed of 10 rpm into the kneading chamber heated to a heating temperature of 320 ° C. did. After the powder was completely introduced into the kneading chamber, the mixer rotation speed was increased to 300 rpm and melt kneading treatment was performed for 10 minutes. In this operation, a significant torque increase was observed from the time when the kneading time passed 6 minutes, and the final kneading torque reached twice that immediately after the kneading rotation speed was increased to 300 rpm, resulting in oxidation crosslinking of PAS (that is, deterioration of the resin component). It was estimated that The obtained particle-dispersed PAS composition was recovered.

(Comparative Example 2: Preparation of composite by melt kneading method, equivalent to comparison of Example 2)
The same operation as in Comparative Example 1 was performed except that instead of the copper (II) chloride dihydrate powder in Comparative Example 1, the iron (III) powder was changed to 0.50 g. In this operation, a light chlorine odor was generated during the kneading operation. In addition, a significant torque increase was observed from the time when the kneading time was 5 minutes, and the final kneading torque reached three times that immediately after the kneading rotation speed was increased to 300 rpm, resulting in PAS oxidation crosslinking (that is, deterioration of the resin component). It was estimated that The obtained particle-dispersed PAS composition was recovered.

(Comparative Example 3: Preparation of PAS composition by melt kneading method, Patent Document 1: equivalent to Example 7)
A solution prepared by dissolving 0.66 g of palladium (II) chloride in 100 ml of a water / methanol 1: 1 mixed solution and 100 g of PPS-1 resin powder was mixed, and then the solvent was removed by drying under reduced pressure to remove PPS-1 and palladium chloride ( A mixture of II) was obtained. 5.6 g of this mixture was sampled and melt kneaded by the same operation method as in Comparative Example 1. Even in this kneading operation, an increase in torque in the kneading process was observed, and the kneading torque at the final time reached 2.5 times that immediately after the kneading rotation speed was increased. The obtained particle-dispersed PAS composition was recovered.

(Comparative Example 4: Preparation of PAS composition by melt kneading method, Patent Document 1: equivalent to Example 13)
A particle-dispersed PAS composition was obtained in the same manner as in Comparative Example 3 except that 0.28 g of iron (III) chloride was used instead of palladium (II) chloride. During this operation, a light chlorine odor was generated from the kneader. Further, as in Comparative Examples 1 to 3, an increase in the kneading torque was observed, and the kneading torque at the final time reached twice that immediately after the rotation speed was increased.

  About the nanoparticle dispersion | distribution PAS composition obtained by each said Example and comparative example, after producing the sheet-like measurement sample by the following method, the measurement and test of the following items were performed.

(Preparation of plate-shaped resin composition (sample for measurement))
Using a resin composition obtained in each example and comparative example, and 1.0 g of PAS-1 which has not been subjected to a composite treatment, a 200 μm thick copper plate having a 6 cm square opening is used as a mold, and the thickness is 6 cm square. A 200 μm plate-shaped resin composition was obtained. This plate sample was used for the subsequent measurements.

(Measurement 1) Verification of inorganic component by measurement with fluorescent X-ray and measurement of content rate After cutting various plate-shaped resin compositions prepared by the above method into 3 cm square, the weight is measured, and the density of this composition Was measured. This was set in a measuring holder having an opening of 20 mm in diameter. The sample was subjected to total elemental analysis using a fluorescent X-ray analyzer “ZSX100e” manufactured by RIKEN ELECTRIC CO., LTD. The sheet obtained from PPS-1 contained no metal elements other than a very small amount of Na contained in the synthetic raw material.
By using the obtained results of the total elemental analysis, the sample data of the measurement sample (the given data is sample shape; film, correction component: PPS, mass value per area of the actually measured sample) is given to the apparatus. Included in each nanoparticle-dispersed PAS composition obtained by the FP method (Fundamental Parameter method; a method in which the uniformity of the sample and surface smoothness are assumed and correction is performed using constants in the apparatus and the components are quantified) The metal element ratio (mass%) was calculated.
Also, using the metal element ratio (detected value, mass%) obtained by the above method and the existing ratio (metal element charge ratio, mass%) when the metal element in the inorganic metal compound is compounded 100%. The composite yield (%) was calculated by the following formula.

(Measurement 2) Calculation of Inorganic Average Particle Size by Observation with Scanning Electron Microscope (SEM) The plate-like resin composition was cut out with a razor and set in a SEM holder so that the cross-section became the upper surface. A sample for SEM observation was prepared by depositing 1 nm of Pt thereon. Using a backscattered electron detector in a scanning electron microscope S-3400N (manufactured by Hitachi High-Technology Corporation), the dispersion state of the inorganic fine particles in the cross section was observed at 500 to 20000 times. In this measurement, an inorganic metal compound having a mass heavier than that of the surrounding PAS resin is observed as a bright region. Under this observation condition, particles of a minimum of 40 nm can be observed. 100 particle diameters observed by this method were measured, and the average value was defined as the average particle diameter. In addition, apart from the average particle diameter, when even one coarse particle of 1 μm or more was seen in an arbitrary observation region at 500 times, it was judged that there was a coarse particle, and when it was not seen, there was no coarse particle.

(Measurement 3) Measurement of Melt Viscosity of PAS Composition The melt viscosity (Pa · s) characteristics of the PAS compositions obtained in each of the Examples and Comparative Examples were calculated as follows: Cavity Rheometer Capillograph 1D PMD-C (Corporation) Measured using Toyo Seiki Seisakusho. The measurement conditions are a measurement temperature of 300 ° C., a used capillary φ1 × 10 mm, and a shear rate of 500 sec ⁻¹ .

  Table 1 below summarizes the results of each example and comparative example.

As can be seen in each example of Table 1, in the present invention, an inorganic metal compound is dissolved in an organic solvent capable of dissolving a PAS resin, and then precipitated, whereby a nanoparticle-dispersed PAS composition containing a metal component is obtained. I was able to get it. Furthermore, the yield with respect to the amount of metal added was relatively high at 57% or more, and it was revealed that complexation occurred efficiently. This is because the PAS resin and the inorganic metal compound are dissolved and compounded in an organic solvent, so that the metal component of the inorganic metal compound is swollen by the solvent in a state of being atomized to a minimum in an ionic state. It is considered that the metal components are not lost easily because they enter between the PAS molecular chains and are combined in a bottom-up manner, and further, the combination is performed in a solvent and sealed.
In addition, no coarse particles of micron order were observed and it was confirmed that the composition was homogeneous. Also, the melt viscosity hardly increased from the raw material PAS by the inorganic composite operation.

On the other hand, in Comparative Examples 1 and 2 in which the inorganic metal compound was directly melt-kneaded, the metal components were aggregated with a particle size of 300 nm or more. In addition, micron-order particles were also found. This is thought to be because the inorganic metal compound is compounded from an incompletely dispersed state such as dry blending and cannot be atomized. When a compound having a high decomposition temperature such as copper chloride (II) of Comparative Example 1 is used, the compounding yield is high. However, a compound having a decomposition temperature lower than the melt kneading temperature as in Comparative Example 2 is obtained by a melt kneading operation. The yield was lowered by going out of the system due to sublimation and evaporation before being combined. From this, it became clear that it is difficult to make a composite by melt kneading depending on the material due to the thermal characteristics of the composite material.
Moreover, in the method (based on the Example of Patent Document 1) in which the metal chlorides shown in Comparative Examples 3 and 4 were dissolved in a solvent and mixed with PAS and then the solvent was removed and melt kneading was performed (in accordance with the example of Patent Document 1), the average particle size was Small particles of micron order were also found. This is presumed that there was a portion in which the metal chloride was re-agglomerated during the solvent removal, which did not disperse and formed coarse particles. Further, in Comparative Example 4, as in Comparative Example 2, the yield was low because the kneading temperature was higher than the boiling point of iron (III) chloride.
In any of the comparative examples, since kneading was performed with a strong shear force, the PAS resin was accompanied by an increase in melt viscosity presumed to be oxidized and crosslinked. It has been clarified that the compounding by the melt kneading method has a problem that a small amount of coarse particles are mixed in spite of such strong shearing. Since these coarse particles can be a starting point of destruction in the structural material, even a small amount is not preferable. The present invention has the advantage that such coarse particles do not exist.

Claims (4)

A method for producing a polyarylene sulfide resin composition , in which a polyarylene sulfide resin and an inorganic metal compound are dissolved in an organic solvent capable of dissolving the polyarylene sulfide resin, and then metal element-containing nanoparticles to be deposited are dispersed. ,
The metal component of the metal compound is at least one selected from the group consisting of copper, zirconium, nickel, cobalt and zinc, and the production of the polyarylene sulfide resin composition in which the metal element-containing nanoparticles are dispersed Method.   The method for producing a polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin and the inorganic metal compound are dissolved in an organic solvent capable of dissolving the polyarylene sulfide resin under high temperature sealing. The method for producing a polyarylene sulfide resin composition according to claim 1 or 2 , wherein the organic solvent is N-methyl-2-pyrrolidone. The manufacturing method of the polyarylene sulfide resin composition in any one of Claims 1-3 which uses an autoclave.