JP3417504B2 - Polyarylene sulfide resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition, and more particularly to the above resin composition particularly suitable for a molded article having a welded portion.

[0002]

2. Description of the Related Art In recent years, a thermoplastic resin having high heat resistance and chemical resistance has been required as a material for electric / electronic equipment parts, automobile equipment parts, chemical equipment parts and the like. . Polyarylene sulfides (hereinafter sometimes abbreviated as PAS) represented by polyphenylene sulfides (hereinafter sometimes abbreviated as PPS) have recently attracted attention as one of the resins that meet this demand. However, when the resin is molded, the mechanical strength such as the toughness of the welded portion, that is, the welded portion where the flow front interfaces of two or more resin streams meet and fuse together in the mold cavity becomes extremely low. have. Therefore, there is a problem that the weld portion is broken when it is subjected to thermal stress or mechanical stress. Further, since the resin has too high melt fluidity, it has a problem that burrs are easily generated during molding.

In view of the above problems, Japanese Patent Application Laid-Open No. 57-70157 discloses P having a predetermined melt flow rate and crosslinking rate.
A resin composition in which glass fiber having a specific size is added to AS is disclosed. However, the resin composition does not sufficiently improve the mechanical strength such as the toughness of the weld portion and reduce the burr, and the mechanical strength is insufficient, so that the applicable applications are limited. there were.

Further, JP-A-64-38211 and JP-A-64-6
In JP 3115 and JP-A 64-89208, at least one silane compound selected from the group consisting of aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane and vinylalkoxysilane is added to PAS as a coupling agent. A method is disclosed. However, in this method, improvement of mechanical strength such as toughness of the weld portion and reduction of burrs are not sufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyarylene sulfide resin composition which has a high mechanical strength such as the toughness of the welded portion and is capable of giving a molded product with less burrs. To do.

[0006]

The present invention provides (A) an alkali metal sulfide, a dihaloaromatic compound and a polyhaloaromatic compound in an amount of 0.40 to 0.80 mol% based on the charged alkali metal sulfide. A branched polyarylene sulfide obtained by polymerization, having a melt viscosity V ₆ of 500 to 4800 poise and a non-Newton's index N of 1.50 or more. Parts, (B) organosilane compound 0.01 to 10 parts by weight, and (C) inorganic filler 0 to 300 parts by weight.

The resin composition of the present invention is characterized by using PAS having the above-mentioned characteristics and combining it with an organic silane compound. The effect of the present invention cannot be exerted even if PAS not having the above-mentioned characteristics is used or only PAS having the above-mentioned characteristics is used.

PA used in the resin composition of the present invention
S is a known polymer having an arylene sulfide repeating unit, and particularly preferably PPS. In the present invention, the melt viscosity V ₆ of the component (A) PAS is 50
Must be between 0 and 4800 poise. Melt viscosity V ₆
Is preferably 800 poises or higher, particularly preferably 1500 poises or higher, and preferably 4000 poises or lower, particularly preferably 3000 poises or lower. When the melt viscosity is less than the above range, mechanical strength such as toughness in the weld portion is lowered and burrs are remarkably generated during molding. Exceeding the above range is not preferable because the molding processability decreases. here,
Melt viscosity V ₆ is 300 ℃ using a flow tester, load
Viscosity (poise) measured after holding at 20 kgf / cm ² and L / D = 10 for 6 minutes.

The PAS used in the present invention must have a non-Newtonian index N of 1.50 or more,
It is preferably 1.55 or more. When it is less than the above value, mechanical strength such as toughness in the weld portion is deteriorated and burrs are remarkably generated during molding, which is not preferable. The upper limit is not particularly limited. Here, the above non-Newtonian index N is L / D at 300 ° C. by using a capillograph.
It is a value calculated by measuring the shear rate and the shear stress under the condition of = 40 and using the following formula (I). An N value of 1 indicates a Newtonian fluid, and an N value of more than 1 indicates a non-Newtonian fluid.

[0010]

## EQU1 ## SR = K.SS ^N (I) (where SR is the shear rate (sec ^-1 ), SS is the shear stress (dyne / cm ² ), and K is a constant.) The above PAS is It can be preferably produced by the following production method.

That is, in the method for producing PAS by reacting an alkali metal sulfide and a dihalo aromatic compound in an organic amide solvent, the molar ratio of the alkali metal sulfide and the dihalo aromatic compound is 0.940 to. 1.000,
Furthermore, 0.40 to 0.8 with respect to the charged alkali metal sulfide
By adding 0 mol% of polyhaloaromatic compound into the polymerization reaction system, and cooling the gas phase part of the reaction vessel during the reaction, a part of the gas phase in the reaction vessel was condensed to form a liquid phase. Bring to reflux.

In the above production method, the molar ratio of the alkali metal sulfide to the dihaloaromatic compound is 0.940 to 1.000,
It is preferably 0.950 to 0.980. Below the above range,
The burr generated during molding becomes large. Exceeding the above range is not preferable because the workability during molding is reduced.

[0013] In the above manufacturing method, polyhaloaromatic compound added to the polymerization reaction system is to charged alkali metal sulfide 0. It is 40 to 0.80 mol%. If the amount is less than the above range, the non-Newtonian index N in the generated PAS decreases, and the burr generated during molding increases. Exceeding the above range is not preferable because the workability during molding is reduced.

The method of adding the polyhaloaromatic compound into the polymerization reaction system is not particularly limited. For example, the alkali metal sulfide and the dihaloaromatic compound may be added at the same time, or the polyhaloaromatic compound may be dissolved in an organic solvent such as N-methylpyrrolidone at any time during the reaction, and the reaction vessel may be heated with a high pressure pump. You may press fit in.

As a method for producing PAS by cooling a part of the gas phase in the reaction can by condensing a part of the gas phase in the reaction can and then refluxing it to a liquid phase, JP-A-5-22 can be used.
The method described in JP 2196 can be used.

The refluxed liquid has a high water content compared to the liquid-phase bulk because of the difference in vapor pressure 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, the residual alkali metal sulfide (for example, Na ₂ S), alkali metal halide (for example, NaCl), oligomer and the like are contained in a large amount in the layer. In the conventional method, in the state where the generated PAS and the raw materials such as Na ₂ S and byproducts are uniformly mixed at a high temperature of 230 ° C. or higher, not only a high molecular weight PAS cannot be obtained but Depolymerization of PAS also occurred, and thiophenol by-product was observed. However, in the present invention, by positively cooling the gas phase portion of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper portion of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. Of high molecular weight PA
It seems that S 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 this method, it is not necessary to add water during the reaction. However, the addition of water is not excluded at all. However, with the addition of water, some of the advantages of this method are lost. Therefore,
Preferably, the total amount of water in the polymerization reaction system is constant during the reaction.

The gas phase portion of the reaction can 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. Therefore, the water-rich mixture accumulates above 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 so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount, if necessary. 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 moles, 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.

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-step reaction, it is desirable to carry out the cooling from the first step reaction, but it is preferable to perform the cooling from the middle of the temperature rise after the completion of the first step reaction at the latest. 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 device used in each case, operating conditions, and the like.

The organic amide solvent used here is PA
Known for S-polymerization, such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with N-methylpyrrolidone 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.
Although it can be selected from those described in JP-A-3368, p-dichlorobenzene is preferable. In addition, a small amount (20 mol%
A copolymer can be obtained by using one or more kinds of para, meta, or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl of the following). For example, m-dichlorobenzene, o-dichlorobenzene, p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'- These are dichlorodiphenyl sulfone, m, m'-dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl and m, m'-dichlorobiphenyl.

The polyhaloaromatic compound is a compound having three or more halogen substituents in one molecule, for example, 1,2,
3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,
3,5-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro- 2,4,6-trimethylbenzene, 2,2 ', 4,4'-tetrachlorobiphenyl, 2,2', 6,6'-tetrabromo-3,3 ', 5,5'-tetramethylbiphenyl, 1 2,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene and the like and mixtures thereof, 1,2,4-trichlorobenzene, 1,
3,5-trichlorobenzene is preferred.

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

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

Further, in the present invention, the PAS obtained as described above may preferably be further subjected to an acid treatment. The acid treatment is performed at a temperature of 100 ° C. or lower, preferably
It is carried out at a temperature of 40-80 ° 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 precipitated 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 after the acid treatment.
It is 4.0 to 5.0. By adopting the above-mentioned concentration and pH, -SNa and -CO in PAS which is the object to be treated
Most of the ONa terminals can be converted to -SH and -COOH terminals, and at the same time, 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 is preferably 5
It is at least 10 minutes, particularly preferably at least 10 minutes. Below the above, the -SNa and -COONa ends in PAS are replaced by -S.
It is not preferable because the H and --COOH terminals cannot be fully converted. Examples of the acid treatment include acetic acid, formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid,
Carbonic acid or the like is used, with acetic acid being particularly preferred. 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. Next, examples of the (B) organosilane compound used in the present invention include compounds used as silane coupling agents. For example, alkoxysilanes are preferred, more preferably selected from aminoalkoxysilanes, epoxyalkoxysilanes and mercaptoalkoxysilanes. Examples of the aminoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ- Aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, etc. . Examples of the epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. Examples of the mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. In addition to this, haloalkoxysilane,
For example, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane and the like; isocyanate alkoxysilane, such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane and the like; vinylalkoxysilane, such as vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane and the like can also be used. The above organosilane compounds may be used alone or in combination of two or more.

The organosilane compound (B) is used in an amount of 0.01 parts by weight or more, preferably 0.1 parts by weight or more and 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of (A). . If the blending amount of the organic silane compound is too large, the change in viscosity is large and molding becomes difficult, and if the blending amount is too small, the effect of reducing burrs is small.

The resin composition of the present invention may further contain (C) an inorganic filler as an optional component. The inorganic filler is not particularly limited, but powdery / scaly fillers, fibrous fillers and the like can be used. Examples of the powdery / scaly filler include silica, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate,
Examples thereof include calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads and carbon black. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber,
Examples thereof include silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition to this, a filler such as ZnO tetrapot, metal salt (eg, zinc chloride, lead sulfate, etc.), oxide (eg, iron oxide, molybdenum dioxide, etc.), metal (eg, aluminum, stainless steel, etc.) may be used. it can. These can be used alone or in combination of two or more. The surface of the inorganic filler may be treated with a silane coupling agent or a titanate coupling agent.

The inorganic filler (C) is used in an amount of 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of (A). If the amount of the inorganic filler is too large, the viscosity change may be so large that molding cannot be performed. Further, in order to increase the mechanical strength, it is preferable to add 10 parts by weight or more.

In the resin composition of the present invention, in addition to the above-mentioned components, known additives such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, colorants, and the like may be added, if desired. An antistatic agent or the like can be added.

The method for producing the resin composition of the present invention is not particularly limited. For example, the components are mechanically mixed, melted and kneaded (for example, at about 320 ° C.) in a conventional apparatus such as an extruder, extruded, and pelletized. Can be converted. It is also possible to mix / mold as a masterbatch. Further, each component of the composition may be separately charged into an extruder and melt-mixed.

The resin composition of the present invention is a molding material particularly suitable for moldings having a welded portion. The weld portion is a portion that is molded by an injection molding method, and two or more resin flow interface ends of the resin flows merge and are fused in the mold cavity. The weld portion is likely to occur when the molded product has a void portion or when the wall thickness is changed and the material cannot be unidirectionally flowed from the thick portion to the thin portion. If there are two or more gates, or even if a single-point gate is used, the formation of welds is unavoidable when forming a ring-shaped, circular, or rectangular tubular product. The welded portion can generally be identified by the appearance of linear color unevenness on the surface of the molded product or the appearance of a pattern in which the resin flows merge. The molded product having the weld portion as described above includes, for example, a connector, a coil bobbin as an electronic component, a printed circuit board, a chassis for electronic components, a lamp socket as an electric heating component, a dryer grill, a thermostat base, a thermostat case, and a motor. Brush holder as a part,
Claws for copying machines as precision equipment such as bearings and motor cases, diaphragm parts for cameras, watch cases, timepiece base plates, exhaust gas circulation valves as car parts, carburetors, alternator terminal blocks, tachometer housings, battery housings, etc., or Cleansing frame, insulator, pipe bracket as chemical equipment parts,
There are many functional parts such as pump casings, tower fills, etc. Although these molded products do not always have a weld portion, it is difficult to avoid the weld portion because of their function. Further, the above-mentioned molded product is an example, and the molded product having the weld portion is not limited to these.

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

[0036]

EXAMPLES In the examples, the flow tester used for measuring the melt viscosity was a flow tester CFT manufactured by Shimadzu Corporation.
-500C. The capillograph used for obtaining the non-Newtonian index N is Capillograph 1B-PC manufactured by Toyo Seiki Seisakusho.

In the synthesis example, p-dichlorobenzene (hereinafter sometimes abbreviated as p-DCB), 1,3,
5-trichlorobenzene (hereinafter sometimes abbreviated as 1,3,5-TCB) or 1,2,4-trichlorobenzene (hereinafter 1,
The reaction rate of 2,4-TCB) is calculated from the measurement results by gas chromatography. Where p-D
The reaction rate of CB and 1,3,5-TCB or 1,2,4-TCB was calculated by the following formula.

[0038]

[Equation 2] Reaction rate of p-DCB (%) = (1-weight of residual p-DCB / weight of charged p-DCB) x 100

[0039]

[Equation 3] Reaction rate (%) of 1,3,5-TCB (1,2,4-TCB) =       [1-residual 1,3,5-TCB (1,2,4-TCB) weight /                     Charged 1,3,5-TCB (1,2,4-TCB) weight] × 100

[0040]

[Synthesis Example 1] In a 150-liter autoclave, 19.222 kg of flaky sodium sulfide (60.9 wt% Na ₂ S) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 45.
0 kg was charged. While stirring under a nitrogen stream, the temperature was raised to 204 ° C., and 4.600 kg of water was distilled off (the residual water content was 1.08 mol per mol of sodium sulfide). Then, the autoclave was sealed and cooled to 180 ° C, and p-DCB 23.211
kg (the molar ratio of Na ₂ S and p-DCB is about 0.950) and N
MP 18.0 kg was charged. The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. Liquid temperature 22
At 0 ° C on a coil wrapped around the top of the autoclave
Cooling was performed by flowing a refrigerant at 80 ° C. Next, 1,3,5-TCB 0.218
kg (about 0.8 mol% with respect to sodium sulfide) NMP
What was dissolved in 0.5 kg was pressed into an autoclave with a small high-pressure pump. After that, the temperature is raised to 3 at the liquid temperature of 260 ° C.
The mixture was stirred for a time, then 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 obtained slurry was filtered and washed with warm water twice by a conventional method, and then dried at 120 ° C. for about 5 hours in a hot air circulation dryer to obtain a white powdery product. The obtained PPS
The melt viscosity V ₆ (designated R-1) was 2820 poise and the non-Newtonian index N was 1.60.

The reaction rate of p-DCB is 97.8%,
The reaction rate of 1,3,5-TCB was 100%.

[0043]

[Synthesis Example 2] Flake-shaped sodium sulfide (60.1 wt% Na ₂ S) 19.478 kg and NM were placed in a 150-liter autoclave.
P 45.0 kg was charged. 204 with stirring under nitrogen stream
The temperature was raised to 0 ° C., and 5.072 kg of water was distilled off (the residual water content was 1.0 mol per mol of sodium sulfide). After that, the autoclave is sealed and cooled to 180 ° C, and p-DCB2
2.732 kg (the molar ratio of Na ₂ S and p-DCB is about 0.970
), 0.12 kg of 1,2,4-TCB (about 0.55 mol% with respect to sodium sulfide) and 18.0 kg of NMP.
The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 215 ° C. for 7 hours, a refrigerant at 20 ° C. was passed through a coil attached to the outer upper part of the autoclave to cool the gas phase portion of the autoclave. After that, the temperature was raised, the liquid temperature was maintained at 260 ° C., the mixture was stirred for 3 hours, then 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 8.69 kg / cm ²
It was G.

The obtained slurry was treated in the same manner as in Synthesis Example 1 to obtain a white powder product. Obtained PPS (R-2
The melt viscosity V ₆ is 3830 poise and the non-Newtonian index N is 1.55.

The reaction rate of p-DCB is 98.5%,
The reaction rate of 1,2,4-TCB was 100%.

[0046]

[Synthesis Example 3] Into a 150-liter autoclave, 19.222 kg of flaky sodium sulfide (60.9 wt% Na ₂ S) and NM
P 45.0 kg was charged. 204 with stirring under nitrogen stream
The temperature was raised to ° C, and 4.600 kg of water was distilled off (the amount of residual water was 1.08 mol per mol of sodium sulfide). After that, the autoclave is sealed and cooled to 180 ° C, and p-DCB2
1.835 kg (Molar ratio of Na ₂ S and p-DCB is about 1.005
), 1,3,5-TCB 0.109 kg (approx. To sodium sulfide
0.4 mol%) and 18.0 kg NMP. Liquid temperature 15
The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at 0 ° C. While stirring at a liquid temperature of 220 ° C. for 3 hours, a cooling medium of 80 ° C. was flowed around the coil wound around the upper part of the autoclave to cool it. After that, the temperature was raised, the liquid was stirred at 260 ° C. for 3 hours, then 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 8.73k
It was g / cm ² G.

The obtained slurry was treated in the same manner as in Synthesis Example 1 to obtain a white powdery product. Obtained PPS (RC
1)) had a melt viscosity V ₆ of 8750 poise and a non-Newtonian index N of 1.44.

The reaction rate of p-DCB is 99.2%,
The reaction rate of 1,3,5-TCB was 100%.

[0049]

[Synthesis Example 4] 19.478 kg of flaky sodium sulfide (60.1% by weight Na ₂ S) and NM were placed in a 150-liter autoclave.
P 45.0 kg was charged. 204 with stirring under nitrogen stream
The temperature was raised to 0 ° C., and 5.072 kg of water was distilled off (the residual water content was 1.0 mol per mol of sodium sulfide). After that, the autoclave is sealed and cooled to 180 ° C, and p-DCB2
2.386 kg (the molar ratio of Na ₂ S and p-DCB is about 0.986
), 1,3,5-TCB 0.0408 kg (about 0.15 mol% with respect to sodium sulfide) and NMP 18.0 kg were charged.
The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 215 ° C. for 7 hours, a refrigerant at 20 ° C. was passed through a coil attached to the outer upper part of the autoclave to cool the gas phase portion of the autoclave. After that, the temperature was raised, the liquid was stirred at 260 ° C. for 3 hours, then 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 8.69 kg / cm ² G.

The obtained slurry was treated in the same manner as in Synthesis Example 1 to obtain a white powder product. Obtained PPS (RC
The melt viscosity V ₆ of the 2 hereinafter) is 2120 poise, the non-Newtonian index N is 1.29.

The reaction rate of p-DCB is 98.6%,
The reaction rate of 1.3,5-TCB was 100%.

[0052]

[Synthesis Example 5] The same as Synthesis Example 1 except that the addition amount of 1,3,5-TCB was set to 0.1343 kg (about 0.5 mol% with respect to sodium sulfide) and the upper part of the autoclave was not cooled. Carried out. The maximum pressure during the reaction is 10.88 kg / cm ²
It was G.

The obtained slurry was treated in the same manner as in Synthesis Example 1 to obtain a white powdery product. Obtained PPS (RC
The melt viscosity V ₆ of the 3 and referred) is 460 poise, the non-Newtonian index N was 1.40.

The reaction rate of p-DCB is 98.1%,
The reaction rate of 1,3,5-TCB was 100%.

[0055]

Examples 1 to 5 and Comparative Examples 1 to 8 Each PPS obtained in Synthesis Examples 1 to 5, an organic silane compound, and optionally glass fiber were blended in a ratio shown in Table 1, and a Henschel mixer was used for 5 minutes. After premixing, a 30 mmφ twin-screw extruder was used to melt-extrude at a cylinder temperature of 320 ° C. and a rotation speed of 250 rpm to prepare pellets. The resulting pellets were molded by an injection molding machine set at a cylinder temperature of 320 ° C and a mold temperature of 130 ° C, and test pieces were prepared and subjected to various properties tests.

Various characteristics were evaluated by the following test methods.・ Welding strength: width 100 mm x length 170 mm x thickness 2 mm
Was molded using a mold having film gates on both sides, and then cut into pieces having a width of 20 mm, and the tensile strength was measured and evaluated according to ASTM D638.・ The burr characteristics are width 20 mm, length 80 mm, thickness 3 mm,
A connector having 16 pin holes and a pin hole size of 2 × 2 mm was molded, and the burr length generated in the pin hole portion (gap 20 μm) was measured and evaluated.

The above results are shown in Table 1.

[0058]

[Table 1] From Table 1, Comparative Example 1 in which the organosilane compound is not blended has a lower weld strength (tensile strength) and a longer burr length than those of Examples 1 to 3. It is noted that, similarly, in Comparative Example 5 in which the organosilane compound is not mixed, the burr length is longer than that in Example 5. In Comparative Example 2 in which the organosilane compound was blended in an excessively large amount,
The melt viscosity becomes high, making molding difficult. Comparing Comparative Example 3 and Example 4 in which the inorganic filler is blended,
Comparative Example 3 in which the organosilane compound was not blended had a lower weld strength and a longer burr length than Example 4. Comparative Example 4 is an example in which the inorganic filler is excessively blended, and it can be seen that if the inorganic filler is excessive, the melt viscosity becomes high and molding becomes difficult. Comparing Comparative Examples 6 to 8 using PAS having no PAS characteristic of the present invention with Example 1, Comparative Example 6 has a high melt viscosity and is difficult to mold, and Comparative Example 7 has a burr length. In Comparative Example 8, the weld strength is low and the burr length is long.

[0059]

EFFECTS OF THE INVENTION The resin composition of the present invention can provide a molded product having high mechanical strength such as toughness of the weld portion and less burrs.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kanichi Kido 3-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Tonen Kagaku Co., Ltd. Technical Development Center (56) Reference JP-A-59-204657 JP-A-64-89208 (JP, A) JP-A-3-50265 (JP, A) JP-A-64-38211 (JP, A) JP-A-64-6315 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 81/02 C08G 75/02-75/04

Claims (5)

(57) [Claims] 1. 0.40 based on (A) alkali metal sulfide, dihaloaromatic compound and charged alkali metal sulfide
The 0.80 mole% of polyhalo aromatic compound obtained by copolymerizing, a polyarylene sulfide which is branched or melt viscosity V ₆ is 500-4800 poise, and non-Newtonian index N is A resin composition containing 100 parts by weight of a high molecular weight polyarylene sulfide having a molecular weight of 1.50 or more, (B) an organic silane compound (0.01 to 10 parts by weight), and (C) an inorganic filler (0 to 300 parts by weight). 2. The (A) polyarylene sulfide is produced by cooling a gas phase part of a reaction vessel during the reaction to condense a part of the gas phase in the reaction vessel and refluxing the condensed gas to a liquid phase. the resin composition of claim 1, wherein to those were. 3. (A) In the polyarylene sulfide according to claim 1 or 2 resin composition according melt viscosity V ₆ is 800 to 4000 poise. Wherein (B) an organic silane compound, an amino alkoxy silane, epoxy alkoxy silane, and mercapto alkoxysilane is a silane compound selected from the silane according to claim 1 resin composition according to any one of the three. 5. A molded article having a welded portion.
The resin composition according to any one of to 4 .