JPH08231852A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE: To obtain a PAS resin composition having excellent water repellency. CONSTITUTION: The composition comprises 100 pts.wt. substnatially noncross- linked polyarylene sulfide having a weight-average molecular weight of 45000-100000 and 0.1-10 pts.wt. modified and/or unmodified polyorganisiloxanes.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin composition, and more particularly to a PAS resin composition having excellent water repellency.

[0002]

2. Description of the Related Art PAS has excellent heat resistance and molding processability, and further has good chemical resistance, flame retardancy, dimensional stability and the like. Therefore, it is widely used for electric / electronic parts or mechanical parts. Further, PAS is useful as a container for containing a chemical solution or ultrapure water in the field of electronic materials and the like. At this time, the PAS is required to have water repellency.

However, PAS obtained by crosslinking a low molecular weight PAS (Japanese Patent Publication No. 45-3368) by a conventional method by thermal oxidation is inferior in water repellency.

As a method for improving the water repellency of PAS,
JP-A-63-213561 discloses adding polytetrafluoroethylene to PAS. However, this method has a drawback that the mechanical strength is lowered.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a PAS resin composition having excellent water repellency.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, they have found that the above problems can be solved by blending a polyorganosiloxane into a substantially non-crosslinked PAS having a predetermined weight average molecular weight, and have completed the present invention.

That is, the present invention comprises (A) 100 parts by weight of a substantially non-crosslinked polyarylene sulfide having a weight average molecular weight of 45,000 to 100,000 and (B) a modified and / or unmodified polyorgano. Siloxane
A polyarylene sulfide resin composition containing 0.1 to 10 parts by weight.

Component (A) PA used in the present invention
The weight average molecular weight of S is 45,000 to 100,000.
0, preferably 50,000 to 80,000, particularly preferably 53,000 to 70,000. When the weight average molecular weight is less than the above lower limit, the water repellency of the composition becomes poor.
If the amount exceeds the upper limit, the fluidity is poor, and therefore the injection speed and injection moldability are deteriorated, which is not preferable. Further, the PAS has a substantially non-crosslinked structure. A combination of high-molecular weight PAS and polyorganosiloxane obtained by thermal oxidation treatment of low-molecular weight PAS produced by the method of JP-B-45-3368 gives a PAS resin composition having excellent water repellency. I can't get it. In the present invention, PAS having a substantially linear molecular structure is preferably used.

Preferably, the component (A) PAS is prepared by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent and cooling the gas phase portion of the reaction vessel during the reaction. Was produced by condensing a part of the gas phase of the above and refluxing it in the liquid phase. The PAS is
It can be produced by the method described in JP-A-5-222196.

In the above method, the refluxed liquid has a high water content compared to the liquid phase bulk because of the vapor pressure difference between water and the amide solvent. This reflux liquid having a high water content forms a layer having a high water content on the reaction solution. As a result, residual alkali metal sulfides (eg Na ₂ S), alkali metal halides (eg NaCl), oligomers etc.
It will be contained more in the layer. In the conventional method, at a high temperature of 230 ° C. or higher, the generated PAS and the raw materials such as Na ₂ S and the by-products are uniformly mixed,
Not only high-molecular-weight PAS cannot be obtained, but depolymerization of PAS produced with great care also occurs, and by-production of thiophenol is observed. However, in the present invention, by positively cooling the gas phase part of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper part of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. It seems that these factors can be eliminated with high efficiency and high molecular weight PAS can be obtained. However, the present invention is not limited only to the effects due to the above-mentioned phenomenon, and high-molecular weight PAS can be obtained by various influences caused by cooling the gas phase portion.

In the present invention, it is not necessary to add water during the reaction unlike the conventional method. However, the addition of water is not excluded at all. However, some of the advantages of the present invention are lost if the operation of adding water is performed. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The gas phase portion of the reactor can be cooled by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium into an internal coil installed in the upper part of the reaction can, a method of flowing a cooling medium into an external coil or jacket wound around the upper part of the outside of the reaction can, and a reflux condenser installed in the upper part of the reaction can are used. The method may be such as sprinkling water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction can. Any method is effective as long as it has the effect of increasing the reflux amount in the can. May be used. If the outside air temperature is relatively low (for example, room temperature), it is also possible to perform appropriate cooling by removing the heat insulating material conventionally provided on the upper part of the reaction can. In the case of external cooling, water condensed on the reactor wall surface
The amide-based solvent mixture enters the liquid phase along the wall of the reaction vessel. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels along the surface of the cooling device or the wall of the reaction vessel into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230 to 275 for constant temperature
It is preferable to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C. and the time is 1 to 6 hours. To obtain higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. This 2
When carrying out the stepwise operation, the first step is preferably carried out at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too slow, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too fast, PAS having a sufficiently high molecular weight cannot be obtained, and the side reaction rate remarkably increases. The end of the first stage is
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out at a time of mol% and a molecular weight in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo-aromatic compound in the polymerization reaction system is 2 mol% to 15 mol% and the molecular weight is 5,000 to 15,000. Residual rate is 40 mol%
When it is more than 1, the side reaction such as depolymerization is likely to occur in the second step reaction, while when it is less than 1 mol%, the high molecular weight P is finally obtained.
It is difficult to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
At a temperature higher than 270 ° C., side reactions such as depolymerization are likely to occur, making it difficult to stably obtain a high molecular weight product.

As an actual operation, first, dehydration or water addition is carried out in an inert gas atmosphere, if necessary, so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount. The water content is preferably alkali metal sulfide 1
The amount is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol per mol. If it exceeds 2.5 mols, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction and the degree of polymerization will not increase. If it is less than 0.5 mol, the reaction rate is too fast to obtain a sufficiently high molecular weight product, and unfavorable reactions such as side reactions occur.

In the case of the one-step reaction at a constant temperature, the cooling of the gas phase portion during the reaction is preferably performed from the start of the reaction, but it must be performed at least during the temperature increase of 250 ° C. or less. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest after the completion of the first-stage reaction. Regarding the degree of cooling effect, the pressure inside the reaction vessel is usually the most suitable index. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the water content in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, as compared with the case of not cooling under the same reaction conditions, if the reactor pressure is decreased, the amount of reflux liquid is increased, which means that the temperature at the reaction solution gas-liquid interface is decreased. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer having no water content. Therefore, it is preferable to cool the reactor so that the internal pressure of the reactor becomes lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.

The organic amide solvent used here is PA
Known for S polymerization, for example N-methylpyrrolidone (NMP), N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with NMP being preferred. They all have a lower vapor pressure than water.

Alkali metal sulphides are also known, for example lithium sulphide, sodium sulphide, potassium sulphide, rubidium sulphide, cesium sulphide and mixtures thereof. These hydrates and aqueous solutions may be used. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

The dihalo-aromatic compound is, for example, Japanese Patent Publication No.
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using a small amount (20 mol% or less) of one or more kinds of para, meta or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl. For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'-dichlorodiphenyl sulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
It is dichlorobiphenyl.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
A polyhalo compound such as trichlorobenzene can also be used in a concentration of preferably 5 mol% or less based on the total amount of para and metadihalo aromatic compounds.

Further, as a small amount of other additives, a terminal terminating agent and a monohalo compound as a modifying agent can be used in combination.

The PAS thus obtained is separated from by-products by post-treatment methods known to those skilled in the art.

In the present invention, the PAS obtained as described above may be further acid-treated. The acid treatment is carried out at a temperature of 100 ° C. or lower, preferably 40 to 80 ° C. If the temperature exceeds the above upper limit, the PAS molecular weight after acid treatment decreases, which is not preferable. On the other hand, if the temperature is lower than 40 ° C., the remaining inorganic salt is deposited to reduce the fluidity of the slurry and hinder the continuous treatment process, which is not preferable. The concentration of the acid solution used for the acid treatment is preferably 0.01 to 5.0% by weight. The pH of the acid solution is preferably 4.0 to 5.0 after the acid treatment. By adopting the above concentration and pH, -SNa and-in PAS, which is the object to be treated,
Most of the COONa ends can be converted to -SH and -COOH ends, and corrosion of plant equipment and the like can be prevented, which is preferable. The time required for the acid treatment depends on the acid treatment temperature and the concentration of the acid solution, but it is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. When it is less than the above, the -SNa and -COONa terminals in PAS cannot be sufficiently converted to the -SH and -COOH terminals, which is not preferable. For the acid treatment, for example, acetic acid, formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfuric acid, nitric acid, boric acid, carbonic acid, etc. are used, and acetic acid is particularly preferable. By carrying out the treatment, sodium as an impurity in PAS can be reduced. Therefore, it is possible to suppress sodium elution and deterioration of electric insulation during use of the product.

The PAS (A) of the present invention comprises the PAS having a substantially linear molecular structure obtained as described above,
Further, it may be heat-treated in a gas-phase oxidizing atmosphere. By using the above PAS, PAS after heat treatment
Also can maintain a substantially linear molecular structure.
At this time, the PAS used for the heat treatment has a weight average molecular weight of preferably 30,000 to 60,000, particularly preferably 35,000 to 50,000. If it is less than the above lower limit, the PAS weight average molecular weight after the heat oxidation treatment is small, and good water repellency cannot be obtained for the composition. When the amount exceeds the upper limit, the PAS weight average molecular weight after the heat oxidation treatment is large and the fluidity is deteriorated, which is not preferable.

The heat treatment can be carried out by a known method. The heat treatment temperature is preferably 10
0 to 280 ° C, particularly preferably 170 to 250 ° C. If the temperature is lower than the above range, the time required for the heat treatment increases, and if it exceeds the above range, the thermal stability during melting is poor. The time required for the thermal oxidation treatment varies depending on the heating temperature or the desired weight average molecular weight of PAS, but is preferably 0.5 to 25 hours, particularly preferably 5 to 20 hours. If the time is less than the above range, a PAS having a desired weight average molecular weight cannot be obtained, and if it exceeds the above range, microgels increase in the treated PAS, which is not preferable.

The above heat treatment is preferably carried out in a gas phase oxidizing atmosphere of an oxygen containing gas such as air, pure oxygen or the like or a mixture of any of these with any suitable inert gas. Examples of the inert gas include water vapor, nitrogen, carbon dioxide and the like, or a mixture thereof. The concentration of oxygen in the oxygen-containing gas is preferably 0.5 to 50% by volume, particularly preferably 10 to 25% by volume. When the oxygen concentration exceeds the above range, the radical generation amount increases, the viscosity at the time of melting becomes remarkable, and the hue becomes dark, which is not preferable. When the oxygen concentration is less than the above range, the thermal oxidation rate becomes slow, which is not preferable.

An apparatus for performing the heat treatment may be a batch type or a continuous type, and a known apparatus can be used. For example, a device for bringing PAS into contact with an oxygen-containing gas in a closed container equipped with a stirrer can be mentioned, and a fluidized bed thermal oxidation treatment device equipped with a stirrer is preferably used. By using the device, the temperature distribution in the tank can be narrowed. As a result, the thermal oxidation can be promoted and the non-uniform molecular weight can be prevented.

As the component (B) modified and / or unmodified polyorganosiloxane in the present invention, those described below can be used.

As the unmodified polyorganosiloxane,
Preferred are polydimethylsiloxane and / or polymethylphenylsiloxane, and examples of the latter include polydimethyl-diphenylsiloxane copolymer, polydimethyl-phenylmethylsiloxane copolymer, polymethylphenyl-diphenylsiloxane copolymer and the like.

The modified polyorganosiloxane is obtained by modifying a part of the unmodified polyorganosiloxane with a functional group. The functional group preferably includes a hydroxyl group, amino group, carboxyl group, epoxy group, methacryloxy group, mercapto group and the like. For example,
Terminal silanol polydimethylsiloxane, terminal silanol polydimethyldiphenylsiloxane, terminal carbinol polydimethylsiloxane, terminal hydroxypropyl polydimethylsiloxane, polydimethylhydroxyalkylene oxide methylsiloxane, terminal acetoxypolydimethylsiloxane, terminal dimethylaminopolydimethylsiloxane, terminal ethoxy Polydimethylsiloxane, terminal stearoxypolydimethylsiloxane, terminal aminopropylpolydimethylsiloxane, aminoalkyl-containing T structure polydimethylsiloxane, terminal carboxypropylpolydimethylsiloxane, carboxypropyl-containing T structure polydimethylsiloxane, terminal glycidoxypropylpolydimethyl Polysiloxane containing T-structure containing siloxane and glycidoxypropyl Hexane, poly-glycidoxypropyl methyl siloxane, poly-glycidoxypropyl methyl -
Dimethylsiloxane Copolymer, Methacryloxypropyl Polydimethylsiloxane with Terminal, Methacryloxypropyl Containing T-Structure Polydimethylsiloxane, Polydimethyl-
Methacryloxypropylmethylsiloxane, mercaptopropyl-containing T-structure polydimethylsiloxane, polymercaptopropylmethylsiloxane and the like can be mentioned. These may be used alone or in combination of two or more.

The viscosity of these unmodified and modified polyorganosiloxanes is preferably 10 to 5,000 at 25 ° C.
It is preferably 10,000 centistokes, and more preferably high viscosity.

The above polyorganosiloxane is PAS,
Alternatively, it may be graft-polymerized with an olefin-based or vinyl-based polymer. Examples of the olefin-based or vinyl-based polymer to be graft-polymerized include ethylene-methacrylate copolymers, ethylene-vinyl acetate copolymers, polyethylene, polyacrylonitrile and the like. The graft ratio may be in the range that does not impair the excellent heat resistance, chemical resistance, etc. inherent in PAS. The polyorganosiloxane content is preferably 30% by weight or more, particularly preferably 4
It is 0% by weight or more.

In the present invention, the component (A) PAS10
Component (B) polyorganosiloxane is contained in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 6.0 parts by weight, and particularly preferably 0.5 to 5.0 parts by weight, relative to 0 parts by weight. If the component (B) is less than the above lower limit, the water repellency will be poor. When the amount exceeds the upper limit, the water repellency is deteriorated, the original properties of PAS such as the decrease in heat resistance are impaired, and the surface of the molded product becomes cloudy, resulting in a poor appearance.

The compounding method of (A) PAS and (B) polyorganosiloxane is not particularly limited, and a generally widely used method can be used. For example, a method of mixing each component using a Henschel mixer or the like, kneading using a single-screw or twin-screw extruder, and extruding into pellets for molding, or the component (B) from the side feeder port of the extruder. Is added as it is or together with a liquid such as isopropyl alcohol, or supported on an inorganic solid such as zeolite or an organic solid such as a stearic acid derivative, and is further grafted with PAS or the other polymer to prepare a masterbatch. However, a method of blending this may be mentioned.

Further, conventional additives can be added to the PAS resin composition of the present invention. For example, silica as an inorganic filler, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium oxide, magnesium phosphate, silicon nitride, Granular, powdery or scaly ones such as glass, hydrotalcite and zirconium oxide, or fibrous ones such as glass fibers, potassium titanate fibers, carbon fibers and mica ceramic fibers can be blended. These inorganic fillers can be used alone or in combination of two or more. Also,
These inorganic fillers may be treated with a silane coupling agent or a titanate coupling agent. The blending ratio of the filler is preferably 0.01 with respect to 100 parts by weight of PAS, from the viewpoints of the above mechanical strength and moldability.
To 400 parts by weight, particularly preferably 1 to 25 parts by weight.

Further, if necessary, additives such as an antioxidant, a heat stabilizer, a lubricant, a release agent and a coloring agent may be added.

The injection-molded container of the present invention is the PAS of the present invention.
It can be produced from the resin composition using a known injection molding machine and method.

The injection-molded container is excellent in water repellency, and is an etching tank for containing a chemical solution or ultrapure water in the field of electronic materials and the like.
It can be used as a washing tank.

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

[0039]

EXAMPLES In the examples, the weight average molecular weight is obtained by converting the retention time measured at 210 ° C. by gel permeation chromatography using 1-chloronaphthalene as a mobile phase to the standard polystyrene molecular weight and further correcting it by the universal calibration method. Is. The apparatus used was SSC-7000 manufactured by Senshu Scientific.

The contact angle was measured using a goniometer (CA-A type) manufactured by Kyowa Interface Science Co., Ltd. after molding a flat plate having a length of 80 mm, a width of 80 mm and a thickness of 3 mm.

[0041]

Polymerization Example 1 Flake sodium sulfide (61.0 wt% Na ₂ S) 521.4 k was added to a 4 m ³ autoclave.
and 1200 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP). While stirring under a nitrogen stream, the temperature was raised to 204 ° C, and 121.8 kg of water was added.
Was distilled. After that, seal the autoclave 18
After cooling to 0 ° C, paradichlorobenzene (below p-
DCB) 599.0 kg and NMP40
I charged 0 kg. 1 at a liquid temperature of 150 ° C using nitrogen gas
The temperature was started by pressurizing to kg / cm ² G. Liquid temperature is 22
When the temperature reached 0 ° C, the temperature was stopped, stirred at this temperature for 5 hours, then heated again, and when the liquid temperature reached 230 ° C, water was sprinkled with a water sprinkler installed outside the autoclave top. Then, the upper part of the autoclave was cooled. afterwards,
The temperature was continuously raised to a liquid temperature of 260 ° C., and then the reaction was allowed to proceed by stirring at the temperature for 2.5 hours. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction was 8.75 kg / cm ² G.

The resulting slurry was repeatedly filtered and washed with warm water by a conventional method and dried at 130 ° C. for about 4 hours using a hot air dryer to obtain a white powdery PPS having a linear structure. The PPS (P-01) had a weight average molecular weight of 45,400.

Next, the above-mentioned PPS was charged into a thermal oxidation treatment device of 5 m ³ , stirred in an air stream at a tank temperature of 215 ° C. for 9 hours, and then cooled.

The weight average molecular weight of the obtained PPS (P-1) was 64,800.

[0045]

Polymerization Example 2 Flake-shaped sodium sulfide (60.0 wt% Na ₂ S) 521.4 k was added to a 4 m ³ autoclave.
g and 1200 kg of NMP were charged. The temperature was raised to 204 ° C. with stirring under a nitrogen stream to distill 125.4 kg of water. After that, the autoclave was sealed and cooled to 180 ° C, and 596.0 kg of p-DCB and 400 kNMP.
I charged g. 1kg with liquid temperature of 150 ℃ using nitrogen gas
The pressure was increased to / cm ² G and the temperature rise was started. Liquid temperature is 215 ℃
From that point, water was sprinkled with a water sprinkler attached outside the upper part of the autoclave to cool the upper part of the autoclave. Then, the temperature was raised to bring the liquid temperature to 260 ° C., and then the reaction was allowed to proceed by stirring at that temperature for 2 hours. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction is 8.88 kg / cm ²
It was G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method and dried at 130 ° C. for about 4 hours using a hot air dryer to obtain a white powdery PPS having a linear structure. The PPS (P-C01) has a weight average molecular weight of 34,000.
It was 0.

Next, the above PPS was charged into a 5 m ³ thermal oxidation treatment apparatus, stirred in an air stream at a tank temperature of 215 ° C. for 14 hours, and then cooled.

The weight average molecular weight of the obtained PPS (P-2) was 53,600.

[0049]

[Comparative Polymerization Example 1] Flake-shaped sodium sulfide (60.8 wt% Na ₂ S) 525.5 k was added to a 4 m ³ autoclave.
g and 1200 kg of NMP were charged. The temperature was raised to 204 ° C. with stirring under a nitrogen stream, and 124.3 kg of water was distilled off. After that, the autoclave was sealed and cooled to 180 ° C, p-DCB 614.4 kg and NMP 400 k
I charged g. 1kg with liquid temperature of 150 ℃ using nitrogen gas
The pressure was increased to / cm ² G and the temperature rise was started. When the liquid temperature reached 260 ° C., the temperature was stopped and the mixture was stirred for 2 hours to allow the reaction to proceed,
The temperature dropped. Maximum pressure during reaction is 10.60 kg / cm
It was ² G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method and dried at 130 ° C. for about 4 hours using a hot air dryer to obtain a white powdery PPS having a linear structure. The PPS (P-C02) has a weight average molecular weight of 23,60.
It was 0.

Next, the above PPS was charged into a thermal oxidation treatment apparatus of 5 m ³ , stirred in an air stream at a tank temperature of 220 ° C. for 55 hours, and then cooled.

The weight average molecular weight of the obtained PPS (P-C1) was 65,000.

[0053]

[Examples 1 to 4 and Comparative Examples 1 to 7] The PPS obtained as described above was heated at a barrel setting temperature of 310 ° C and a screw rotation speed of 250 rpm using a twin screw extruder of 40 mmφ.
And extruded, and kneaded while dripping polyorganosiloxane [polydimethylsiloxane, viscosity: 60,000 centistokes (25 ° C.)] from the side feed port,
A pellet was made.

A test piece was prepared from the obtained pellets by using an injection molding machine under the conditions of a cylinder set temperature of 320 ° C. and a mold temperature of 130 ° C., and subjected to an evaluation test.

The above results are shown in Table 1.

[0056]

[Table 1] In Examples 1 and 2, the compounding amount of the (B) polyorganosiloxane was changed within the range of the present invention. (B)
It was found that the contact angle was increased and the water repellency was improved by increasing. Example 3 uses (A) PPS having a lower weight average molecular weight within the scope of the present invention as compared to Example 1. The contact angle was almost the same as in Example 1, and excellent water repellency was obtained. Example 4 is before the thermal oxidation treatment when manufacturing the PPS of Example 1. Although the weight average molecular weight was smaller than that of Example 1, good water repellency was obtained.

On the other hand, Comparative Examples 1 to 3 are Examples 1 and 3, respectively.
In (4) and (4), (B) was not blended.
In both cases, the contact angle is extremely low. In Comparative Example 4, the compounding amount of (B) exceeds the range of the present invention under the same conditions as in Example 1. It was found that the contact angle was low and the water repellency was poor. Comparative Examples 5 and 6 are PPS having a weight average molecular weight less than the range of the present invention, that is, Example 3 under the same conditions as in Example 1.
PPS before thermal oxidation treatment when manufacturing PPS used in
And the PPS before the thermal oxidation treatment at the time of manufacturing the PPS used in Comparative Example 7 were used. In each case, the contact angle was extremely low. Comparative Example 7 uses PPS having a crosslinked structure under the same conditions as in Example 1. It was found that the contact angle was low and the water repellency was poor.

[0058]

INDUSTRIAL APPLICABILITY The present invention provides a PAS having excellent water repellency.
A resin composition is provided.

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Claims (7)

[Claims] 1. A weight-average molecular weight of (A) is 45,000 to 1.
A polyarylene sulfide resin composition containing 100 parts by weight of a substantially non-crosslinked polyarylene sulfide of 0,000 and 0.1 to 10 parts by weight of (B) a modified and / or unmodified polyorganosiloxane. 2. A polyarylene sulfide (A) reacts an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, and cools the gas phase portion of the reaction can during the reaction. Part of the gas phase inside is condensed,
It is produced by refluxing this in a liquid phase.
The resin composition described. 3. The resin composition according to claim 1, wherein the polyorganosiloxane (B) is polydimethylsiloxane and / or polymethylphenylsiloxane. 4. The resin composition according to claim 1, wherein the polyarylene sulfide (A) has a weight average molecular weight of 50,000 to 80,000. 5. The (B) polyorganosiloxane is added to 0.3.
The resin composition according to any one of claims 1 to 4, which comprises ˜6.0 parts by weight. 6. The polyarylene sulfide (A) is obtained by further heat-treating the polyarylene sulfide according to claim 2 in a gas phase oxidizing atmosphere.
Alternatively, the resin composition according to any one of 3 to 5. 7. An injection-molded container produced from the polyarylene sulfide resin composition according to any one of claims 1 to 6.