JPH09272801A - Polyarylene sulfide resin molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive polyarylene sulfide resin molding product having a high mechanical strength such as toughness in a welded part. SOLUTION: This polyarylene sulfide resin molding product is obtained by carrying out the injection molding of a resin composition comprising 100 pts.wt. polyarylene sulfide having <=0.7wt.% amount extracted with methylene chloride, 20-15000P melt viscosity V6 and >=15μmol/g content of SX groups (X is an alkali metal or hydrogen atom), 0.01-5.0 pts.wt. epoxy-based silane coupling agent and 0-400 pts.wt. inorganic filler and has a welded part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having a weld portion, which is made of a polyarylene sulfide resin composition.

[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 in the mold cavity is extremely low. It has the drawback that Therefore, there is a problem that the weld portion is broken when it is subjected to thermal stress or mechanical stress.

Therefore, some methods have been proposed so far in order to improve the mechanical strength such as the toughness of the welded portion.

Japanese Patent Publication No. 6-39113 discloses PA
A resin composition containing S, a silane compound such as epoxyalkoxysilane, and an inorganic filler is disclosed. Japanese Patent Publication No. 6-51311 discloses a resin composition containing PAS, aminoalkoxysilane and an inorganic filler. Further, JP-A-1-193360 and JP-A-3-43452 disclose resin compositions containing PAS, ureidosilane and an inorganic filler.
However, in both cases, the reactivity between PAS and the silane compound is not sufficient, and it cannot be said that the mechanical strength such as the toughness of the weld portion is sufficiently improved. Further, in the production of PAS, the reaction is carried out in two steps, and water is added in two steps, a method using an alkali metal carboxylate such as sodium acetate or lithium acetate as a polymerization aid in the reaction system, or a low molecular weight PAS is thermally oxidized to crosslink,
For example, a method for producing high molecular weight PAS is used. Therefore, there are drawbacks such as an increase in the manufacturing cost of the PAS and an insufficient mechanical strength of the PAS.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a polyarylene sulfide resin molded article which has high mechanical strength such as toughness of a weld portion and is inexpensive.

[0007]

The inventor of the present invention has made various studies to solve the above problems. As a result, when the following prescribed PAS is used, it is unexpectedly combined with an epoxy-based silane coupling agent and optionally an inorganic filler, and the mechanical strength such as the toughness of the weld portion is remarkably high, and it is inexpensive. The inventors have found that a molded product can be obtained, and completed the present invention.

That is, according to the present invention, (1) the extraction amount with (A) methylene chloride is 0.7% by weight.
100 parts by weight of a polyarylene sulfide having a melt viscosity V ₆ of 20 to 15,000 poise and an -SX group (X is an alkali metal or a hydrogen atom) of 15 μmol / g or more, (B) epoxy type A polyarylene sulfide resin molded article having a weld part, which is obtained by injection molding a resin composition containing 0.01 to 5.0 parts by weight of a silane coupling agent and 0 to 400 parts by weight of an inorganic filler (C). is there.

In a preferred embodiment, (2) a resin molded product according to the above (1) obtained by injection molding one molded product from two or more gates, (3) (B) epoxy silane cup 0.0 ring agent
The resin molded article according to claim 1 or 2, which contains 5 to 3.0 parts by weight, (4) (B) 0.1 epoxy resin silane coupling agent.
The resin-molded article according to claim 1 or 2, which contains ˜2.0 parts by weight, can be mentioned.

The above-mentioned (A) PAS has many -SX groups. Therefore, it reacts well with many epoxy silane coupling agents. Further, the PAS of the present invention has a small amount of extraction with methylene chloride. Therefore, almost no oligomer having a relatively small molecular weight is present, and the epoxy silane coupling agent is not wasted. From the above, the PAS of the present invention is highly reactive with an epoxy-based silane coupling agent, and a PAS resin molded article having high mechanical strength can be obtained by adding a small amount of the agent.

Further, as described below, the PAS of the present invention is a method in which the reaction is carried out in two steps and water is added in two steps as in the above-mentioned conventional method, or PAS using a polymerization aid in the reaction system. No manufacturing method is used. Therefore, the obtained P
AS is inexpensive.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) PAS of the present invention has an extraction amount with methylene chloride of 0.7% by weight or less, preferably 0.6% by weight or less, particularly preferably 0.5% by weight or less. . The above range is preferable because there are no oligomers having a relatively low molecular weight in PAS. If the amount of extraction exceeds the above upper limit, the effect of improving the mechanical strength such as the toughness of the welded part of the molded article by the epoxy-based silane coupling agent becomes low, which is not preferable. Here, the extraction amount with methylene chloride is a value obtained as follows. 4 g of PAS powder is added to 80 g of methylene chloride, Soxhlet extraction is carried out for 4 hours, then cooled to room temperature, and the methylene chloride solution after extraction is transferred to a weighing bottle. Further, the container used for the above extraction is washed with a total of 60 g of methylene chloride in three times, and the washing liquid is collected and then collected in the weighing bottle. Next, it is determined by heating to about 80 ° C. to evaporate and remove the methylene chloride in the weighing bottle, and weighing the residue.

The (A) PAS has a -SX group (X is an alkali metal or a hydrogen atom) of 15 μmol / g or more, preferably 18 to 35 μmol / g, particularly preferably 20.
~ 30 mol / g. When the group is less than the above lower limit, P
The reactivity between AS and the epoxy-based silane coupling agent decreases. Here, the quantification of the -SX group was performed as follows. After the PAS powder was previously dried at 120 ° C. for 4 hours, 20 g of the PAS powder was added to N-methyl-2-pyrrolidone 150
In addition to g, stir vigorously for 30 minutes at room temperature to eliminate powder agglomerates. Next, after filtering the slurry, washing is repeated seven times using 1 liter of warm water at about 80 ° C. each time. The obtained filter cake is slurried again in 200 g of pure water, and 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Next, after stirring at 25 ° C. for 30 minutes and filtering, washing is repeated 6 times using 1 liter of hot water at about 80 ° C. each time. The resulting filter cake is purified with pure water 2
Reslurry in 00 g and then titrate and quantitate with 1N sodium hydroxide.

Further, (A) PAS has a melt viscosity V ₆ of 2
0 to 15,000 poise, preferably 100 to 10,000
Poises, particularly preferably 400-5000 poises. If it is less than the above lower limit, the original properties of PAS such as mechanical strength cannot be obtained, and the reactivity with the epoxy silane coupling agent is not sufficient, and the mechanical properties such as the toughness of the welded part of the molded article, which is the object of the present invention, are not obtained. It is impossible to achieve the improvement of the physical strength. Exceeding the above upper limit is not preferable because the molding processability decreases. Here, the melt viscosity V ₆ was 300 ° C. under a load of 20 kgf / cm ² , using a flow tester.
It is a value measured after holding for 6 minutes at L / D = 10/1.

In the present invention, (A) PAS is obtained by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent and cooling the gas phase portion of the reaction can during the reaction. The polyarylene sulfide (a) produced by condensing a part of the gas phase inside and refluxing it in the liquid phase can be obtained by washing with an organic solvent and then with water.

Here, the above-mentioned PAS (a) is disclosed in Japanese Patent Laid-Open No.
It can be manufactured by the method described in JP-A-222196.

In this polymerization method, the refluxed liquid has a higher water content than that of the liquid phase bulk because of the vapor pressure difference between water and the amide solvent. The reflux liquid having a high water content forms a layer having a high water content at the upper portion of the reaction solution. As a result, residual alkali metal sulfides (eg Na ₂ S),
Alkali metal halides (eg, NaCl), oligomers, and the like are included in the layer in large amounts. In the conventional method, PAS and N
In a state where the raw materials such as a ₂ S and by-products are uniformly mixed, not only a high molecular weight PAS cannot be obtained, but also
Depolymerization of PAS produced with great care also occurs, and thiophenol by-product is observed. However, in the present invention, the above disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of the water-rich reflux liquid to the upper part of the liquid phase so as to inhibit the reaction. It can be considered that such factors can be effectively eliminated and a high molecular weight PAS can be obtained. However, the present invention is not limited only by the effect of the above phenomenon, but by various effects caused by cooling the gas phase part, high molecular weight PAS
Is obtained.

In this polymerization method, it is not necessary to add water during the reaction unlike the conventional method. However, this does not preclude the addition of water at all. However, if the operation of adding water is performed, some of the advantages of the present invention are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout 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 through an internal coil installed at an upper part in a reaction can, a method of flowing a cooling medium through an external coil or a jacket wrapped around the upper part of the reaction can, and using a reflux condenser installed at the upper part of the reaction can A method such as spraying water or blowing a gas (air, nitrogen, etc.) on the upper portion of the outside of the reaction vessel is conceivable, but any method can be used as long as it has the effect of increasing the amount of reflux in the vessel as a result. May be used. If the outside air temperature is relatively low (for example, normal temperature), appropriate cooling can be performed by removing a heat insulating material conventionally provided on the upper part of the reaction vessel. In the case of external cooling, water condensed on the reactor wall
The amide-based solvent mixture enters the liquid phase along the reaction vessel wall. 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 down the cooling device surface or the reactor wall and 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 preferred 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 for 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 low, 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 phase,
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out the reaction at a time point when the molar% is within the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo aromatic compound in the polymerization reaction system is in the range of 2 mol% to 15 mol%, and the molecular weight is in the range of 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 hard 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
When the temperature is higher than 270 ° C., side reactions such as depolymerization are liable to occur, making it difficult to stably obtain a high molecular weight product.

As a practical 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 the alkali metal sulfide 1
It 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 the amount is less than 0.5 mol, the reaction rate is too high to obtain a product having a sufficient high molecular weight, and undesirable 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. The degree of the cooling effect is usually the most suitable index of the pressure in the reactor. 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, when the pressure in the reaction vessel is reduced as compared with the case where the reaction vessel is not cooled under the same reaction conditions, the amount of the reflux liquid increases, which means that the temperature at the gas-liquid interface of the reaction solution decreases. It is considered that the relative degree of decrease indicates the degree of separation between a layer having a high water content and a layer having no water content. Therefore, it is preferable to perform cooling to such an extent that the internal pressure of the reaction vessel is 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, such as 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. 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 one or more kinds of para-, meta- or ortho-dihalides of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenylsulfone, m, p'-dichlorodiphenylsulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
Dichlorobiphenyl.

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

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

Next, washing of PAS with an organic solvent is preferably carried out by the following method. That is, it is a method of filtering the slurry of PAS (a) produced in the above step and then dispersing the obtained filter cake in an organic solvent. The washing is preferable because the oligomer component having a relatively low molecular weight present in PAS (a) can be removed well.

In one mode of washing, first, the PAS (a) slurry produced in the above step is filtered to obtain a PAS cake. Next, the PAS cake is put into an organic solvent that is preferably 0.5 to 10 times by weight, stirred and mixed at room temperature to 180 ° C. for preferably 10 minutes to 10 hours, and then filtered. The stirring and mixing and filtering operations are preferably repeated 1 to 10 times. Examples of the organic solvent used for the washing include the organic amide-based solvent described in the description of the manufacturing process of PAS (a) above, xylene and the like. An organic amide solvent is preferably used. The organic amide-based solvent may be the same as or different from the one used in the PAS (ii) production process. Particularly preferably, N-methylpyrrolidone is used as the organic amide solvent.

The subsequent washing with water can be carried out according to a known method. However, it is preferably carried out by dispersing the filter cake obtained after washing with the above organic solvent in water. For example, the above filter cake is put into water, preferably 1 to 5 times by weight, stirred and mixed at room temperature to 90 ° C. for preferably 5 minutes to 10 hours, and then filtered. The stirring and mixing and filtering operations are preferably 2
By repeating 10 times, the solvent adhering to PAS and the by-product salt are removed, and the washing with water is completed. By performing water washing as described above, efficient washing can be performed with a smaller amount of water than in a washing method in which water is poured into a filter cake. Further, the present inventor has found that the conventional solvent removal by drying reduces the reactivity between PAS and the epoxy-based silane coupling agent.
However, if solvent removal by washing with water is used as in the present invention, high reactivity between PAS and the epoxy-based silane coupling agent can be maintained.

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 the 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. Further, the pH of the acid solution after the acid treatment is preferably 4.0 to 5.0. By adopting the above concentration and pH, it is possible to convert most of -SY (Y represents an alkali metal) terminal in PAS which is the object to be processed to -SH terminal and to corrode plant equipment. Is preferable because it can prevent The time required for the acid treatment depends on the temperature of the acid treatment and the concentration of the acid solution.
Minutes or more, particularly preferably 10 minutes or more. If it is less than the above, the -SY end in PAS cannot be sufficiently converted to the -SH end, which is not preferable. In the acid treatment, for example, acetic acid,
Formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid, carbonic acid and the like are used, and acetic acid is particularly preferred. By performing the treatment, an alkali metal such as sodium which is an impurity in the PAS can be reduced. Therefore, elution of alkali metal such as sodium during use of the product and deterioration of electrical insulation can be suppressed.

The component (B) epoxy silane coupling agent used in the present invention is preferably γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and the like can be mentioned.

The lower limit of the amount of the component (B) epoxy silane coupling agent compounded is 0.01 part by weight, preferably 0.05 part by weight, and particularly preferably 0, based on 100 parts by weight of the component (A) PAS. 0.1 parts by weight, and the upper limit is 5.
It is 0 part by weight, preferably 3.0 parts by weight, particularly preferably 2.0 parts by weight. If the component (B) is less than the lower limit, the mechanical strength such as toughness of the welded part of the molded product is low, and if it exceeds the upper limit, moldability is deteriorated due to thickening, mechanical strength is decreased, and appearance of the molded product is poor. And cause cost increase, which is not preferable.

The present invention may further contain (C) an inorganic filler as an optional component. (C) The inorganic filler is not particularly limited, and for example, a powdery / flaky filler, a fibrous filler, and the like can be used. Examples of the powdery / flaky filler include alumina, talc, mica, kaolin, clay, titanium oxide, calcium carbonate,
Calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide,
Glass beads, carbon black and the like can be mentioned. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, 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 upper limit of the component (C) inorganic filler is 400 parts by weight, preferably 200 parts by weight, particularly preferably 100 parts by weight, per 100 parts by weight of the component (A) PAS. If the component (C) exceeds the above upper limit, the moldability deteriorates, which is not preferable. In order to increase the mechanical strength, it is preferable to add 0.01 parts by weight or more.

Furthermore, if necessary, in addition to the above components,
Known additives and fillers such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, colorants, and the like can be added.

The method of mixing the above components is not particularly limited. A method generally used widely, for example, a method of mixing the components with a mixer such as a Henschel mixer can be used.

To mold the molded article of the present invention, for example,
It can be easily and economically carried out by melt-kneading the above mixture with a single-screw or twin-screw extruder to once form a pelletized composition, and injection-molding the composition. However, the method is not limited to this, and a method of mixing and molding a part of the necessary components as a masterbatch may be used.

In the present invention, the welded portion is a portion which is molded by an injection molding method and in which the flow front interfaces of two or more resin streams are joined and 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 article of the present invention is preferably obtained by injection molding with injection molding by providing gates at two or more locations in one mold cavity corresponding to one molded article. . An interface (weld part) where two or more resin flows corresponding to the number of gates are joined is necessarily formed in the molded product, and the interface region is wide, and therefore, conventionally, the strength defect of the weld part is also remarkable, There was a fatal obstacle to practical strength. The present invention is particularly effective in ameliorating the remarkable defects in the weld portion which occur in a molded product using such two or more gates.

Examples of the molded product having a welded portion as described above include connectors as electronic parts, coil bobbins, printed circuit boards, chassis for electronic parts, lamp sockets as electric heating parts, dryer grills, thermostat bases, thermostat cases. Etc., brush holders as motor parts, bearings, motor cases, claws for copying machines as precision equipment, diaphragm parts for cameras,
Exhaust gas circulation valves, carburetors, alternator terminal blocks, tachometer housings, battery housings, etc. as watch parts, timepiece base plates, etc., or cleansing frames, insulators, pipe brackets, pump casings, tower fillings etc. as chemical equipment parts. There are many functional parts. It is preferably used as a connector. 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.

[0043]

EXAMPLES In the examples, the melt viscosity V ₆ is a value measured using a flow tester CFT-500C manufactured by Shimadzu Corporation.

Synthesis Example 1 Flake-shaped sodium sulfide (60.7 wt% Na ₂ S) 19.285 kg and N were added to a 150 liter autoclave.
MP45.0kg was charged. While stirring under a nitrogen stream, the temperature was raised to 204 ° C. to distill 4.892 kg of water. Then, the autoclave was sealed and cooled to 180 ° C., and paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) 22.161 kg and NMP 18.0 kg
Was charged. 1kg / using nitrogen gas at a liquid temperature of 150 ℃
The pressure was raised to cm ² G and the temperature rise was started. While stirring at a liquid temperature of 220 ° C. for 5 hours, water was sprinkled by a sprinkler attached to the outside of the upper part of the autoclave to cool the upper part of the autoclave. After that, the temperature was raised to a liquid temperature of 255 ° 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 at the top of the autoclave was stopped. During the cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop.

After filtering the obtained polymerized slurry, the obtained filter cake was slurried in unused NMP (slurry concentration 15% by weight). Then 30 at 120 ℃
Stir for 1 minute, filter to remove NMP, then pour the filter cake into warm water at about 80 ° C. (about 2 times the weight of filter cake by weight) and stir thoroughly for about 30 minutes before filtering. This operation of washing with water and filtration was repeated 7 times. Then, the obtained filter cake was dried in a hot air circulation dryer at 120 ° C. for about 5 hours to obtain PPS in the form of white powder. PPS obtained
The V ₆ of (P-1) was 970 poise.

Synthesis Example 2 The polymerized slurry obtained in the same manner as in Synthesis Example 1 was filtered, and the obtained filter cake was slurried in unused NMP (slurry concentration 15% by weight). Then 120 ° C
Stir at 30 minutes, filter to remove NMP, then filter cake with warm water at about 80 ° C. (about twice filter cake by weight).
It was put into the flask, stirred sufficiently for about 30 minutes, and then filtered. This operation of washing with water and filtration was repeated twice. The obtained filter cake was slurried in pure water, acetic acid was added to the slurry to adjust the pH to 5.0, and the mixture was stirred at 50 ° C. for 30 minutes for acid treatment. The procedure of filtration after acid treatment, addition of pure water, stirring and filtration was repeated four times. Next, the obtained filter cake was dried in a hot air circulation dryer at 120 ° C. for about 5 hours to obtain PPS in the form of white powder. The obtained PP
The V ₆ of S (P-2) was 880 poise.

Synthetic Example 3 (used in Comparative Example) The same procedure as in Synthetic Example 1 was carried out except that washing with unused NMP was not carried out. V of the obtained PPS (P-3)
₆ was 820 poise.

Synthetic Example 4 (Used in Comparative Example) The polymerized slurry obtained in the same manner as in Synthetic Example 1 was filtered, and then the cake was distilled with an evaporator under reduced pressure of 10 torr to remove NMP in an oil bath at 200 ° C. Until it disappears
It was dried for about 1 hour. Then, the mixture was cooled, poured into warm water of about 80 ° C. (about twice the weight of the filter cake by weight), sufficiently stirred for about 30 minutes, and then filtered. This operation of washing with water and filtration was repeated 7 times. Then, the filter cake was dried at 120 ° C. for 5 hours in a hot air circulation dryer to obtain a brown powder product. The V ₆ of the obtained PPS (P-4) was 1020 poise.

Synthesis Example 5 (used in Comparative Example, JP-A-61-7
It is PPS manufactured according to the method of No. 332. (1) First-stage polymerization In a 150-liter autoclave, 19.028 kg of flaky sodium sulfide (60.7 wt% Na ₂ S) and N were added.
MP45.0kg was charged. While stirring under a nitrogen stream, the temperature was raised to 204 ° C., and 4.497 kg of water was distilled off. The residual water content was 1.10 mol per mol of sodium sulfide. Then, the autoclave is closed and
After cooling to ℃, 22.200kg of p-DCB and NM
P18.0 kg was charged and polymerized at 210 ° C. for 10 hours to obtain a prepolymerized slurry (S-1).

The amount of residual p-DCB in the slurry was measured using a gas chromatograph, and p-DC was calculated according to the following formula.
The conversion rate of B was determined. The conversion rate was 95.0 mol%.

[0051]

## EQU1 ## Conversion rate of p-DCB = [p-DCB charging amount (mol) -p-DCB residual amount (mol)] × 100 / p-DC
B charge amount (mol) 100 g of the slurry was taken and suction filtered as it was to remove the liquid component. Then, the solid content was dispersed in about 1 kg of deionized water, and suction filtration was performed again to wash the produced PPS. After repeating such an operation 3 times, at 100 ℃ 2
After drying for an hour (in an air atmosphere), PPS powder was obtained. The P
Melt viscosity of PS was measured at 310 ° C. The shear rate was 60 poise converted to 200 sec ^-1 . (2) Second-stage polymerization Into a 1-liter autoclave, 550 g of slurry (S-1) was added, and 50.4 g of water (total water amount per mol of sodium sulfide was 4.60 mol) was added, and the temperature was set to 250 ° C under a nitrogen atmosphere. The temperature was raised to 3, and polymerization was carried out for 3 hours. p-DCB
The conversion rate was 99.0%. After cooling, pearly PP
S was sieved from NMP, PPS oligomer and the like. Then, the pearl-like PPS was repeatedly washed with deionized water, and then dried in a hot air circulation dryer at 100 ° C. for 3 hours to obtain white pearl-like PPS. The V ₆ of the obtained PPS (P-5) was 1440 poise (310 ° C, shear rate 2
The value measured at 00 sec ^-1 was about 1100 poise).

[0052]

Examples 1 to 5 and Comparative Examples 1 to 4 The amounts (parts by weight) of each PPS, epoxy silane coupling agent and glass fiber (CS 3J-961S, trademark, manufactured by Nitto Boseki Co., Ltd.) shown in Table 1 were used. After premixing with a Henschel mixer for 5 minutes to make it uniform, use a 20 mmφ twin-screw counter-rotating extruder to set the barrel temperature at 300 ° C and the rotation speed at 400.
Pellets were prepared by melt-kneading at rpm and extruding. Further, the width of the resulting pellets is 80 mm by an injection molding machine in which the cylinder temperature is 320 ° C and the mold temperature is 130 ° C.
A flat plate having a length of 180 mm and a thickness of 3 mm was molded using a mold having film gates on both sides. Then, after cutting this into a strip shape with a width of 20 mm, ASTM D
Measure tensile strength according to 638 and ASTM D
The Izod impact strength was measured according to 256 to evaluate the strength of the welded portion.

Here, the epoxy silane coupling agent used in Examples 1 to 4 and Comparative Examples 1 to 4 was γ-glycidoxypropyltrimethoxysilane (A187, trademark, manufactured by Nippon Unicar Co., Ltd.). The epoxy silane coupling agent used in Example 5 was β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane (A186, trademark, manufactured by Nippon Unicar Co., Ltd.).

Table 1 shows the above results.

[0055]

[Table 1] Example 1 was a resin molded product of the present invention and had good weld strength. Example 2 is a molded article manufactured using PPS obtained by further acid-treating the (A) PPS used in Example 1. Similar to Example 1, good weld strength was exhibited. In addition, Examples 3 and 4 are the same as Example 2.
Under the same conditions as described above, a molded product produced by increasing the content of the epoxy-based silane coupling agent (B) within the scope of the present invention. When the content of (B) was increased, the strength of the weld portion was increased. The fifth embodiment is the same as the second embodiment except that the type (B) is changed. As (B), β-
Using (3,4-epoxycyclohexyl) ethyltrimethoxysilane, better weld strength was obtained.

On the other hand, Comparative Examples 1 and 2 both use PPS whose methylene chloride extraction amount exceeds the range of the present invention. As compared with Example 1, the strength of the weld portion was significantly lower. Comparative Example 3 uses PPS in which the -SX group is less than the range of the present invention. Compared with Example 1, the strength of the weld portion was significantly lower. Comparative Example 4
It was molded without blending (B) under the same conditions as in Example 1. Compared with Example 1, the strength of the weld portion was significantly lower.

[0057]

INDUSTRIAL APPLICABILITY The present invention provides a polyarylene sulfide resin molded article which has high mechanical strength such as toughness of a weld portion and is inexpensive.

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Claims (2)

[Claims] 1. The amount of (A) methylene chloride extracted is 0.7.
100% by weight of a polyarylene sulfide having a melt viscosity V ₆ of 20 to 15,000 poise and an -SX group (X is an alkali metal or a hydrogen atom) of 15 μmol / g or more, (B) Polyarylene sulfide resin molding having a weld part obtained by injection molding a resin composition containing 0.01 to 5.0 parts by weight of an epoxy-based silane coupling agent and 0 to 400 parts by weight of an inorganic filler (C). Goods. 2. The resin molded product according to claim 1, which is obtained by injection molding one molded product from two or more gates.