JPH08120081A - High-molecular poly(arylene sulfide) for molded sheet - Google Patents

Abstract

PURPOSE: To obtain an inexpensive high-mol. poly(arylene sulfide) which gives a molded sheet excellent in tensile elongation at break and tensile strength at break. CONSTITUTION: The objective high-mol. poly(arylene sulfide), which is for use in forming a molded sheet, is obtained by heating, in an oxidizing gas atmosphere, a poly(arylene sulfide) produced by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent while cooling the gas phase within the reaction vessel during the reaction to partly condense the gas and refluxing the condensate to the liquid phase.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high molecular weight polyarylene sulfide for a sheet-shaped molded product and a sheet-shaped molded product produced therefrom.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter referred to as P
(Sometimes abbreviated as AS) has excellent resistance to acids, alkalis, various organic solvents and the like. Therefore, PAS is expected to be suitable for use as a sheet, a film, etc., particularly under a high temperature and corrosive environment.

Japanese Patent Publication No. 45-3368 describes a method for producing PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent. However, it was not possible to produce high molecular weight PAS by this method.

Therefore, it has been practiced to produce a high molecular weight PAS by subjecting the above low molecular weight PAS to thermal oxidation treatment and crosslinking. However, such cross-linked PAS is especially
Mechanical strength such as impact resistance and tensile elongation at break was insufficient. Further, since the crystallization rate is high and the resin is rapidly cured during extrusion molding, there is a problem in processing into a sheet-shaped molded body. For example, when the film is formed by the inflation method, it is difficult to obtain a stretched oriented film by curing before the expansion is sufficient, and when a sheet or the like is extrusion-molded by a T-die, before being wound on a take-up roll. It was difficult to obtain a smooth sheet having a certain thickness by curing.

A PAS that can be used for the above applications and a method for manufacturing the same have been proposed. In Japanese Examined Patent Publication No. 4-80053,
PAS with predetermined physical properties suitable for films, sheets, etc.
And its manufacturing method are described. However, the PAS obtained by this method does not have sufficient mechanical strength such as tensile elongation at break. Further, the method is a block copolymer composed of a paraphenylene sulfide polymer and a metaphenylene sulfide polymer, in which a first step of producing a reaction liquid containing the paraphenylene sulfide polymer and a dihaloaromatic compound composed of metadihalobenzene are added. And a second step for producing. Further, the degree of polymerization of the para-phenylene sulfide polymer produced in the first step, the mole fraction of the para-phenylene sulfide polymer in the block copolymer produced in the second step are set to predetermined values, and The reaction is carried out so that the melt viscosity, the glass transition temperature, the crystal melting point and the crystallization index are set to predetermined values. Therefore, the two steps of the first step and the second step are required, and the control of the reaction becomes complicated. Therefore, it is disadvantageous in terms of equipment, economy and operation, and the generated PAS
Will be expensive.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an inexpensive high molecular weight polyarylene sulfide which gives a sheet-shaped molded article having excellent tensile elongation at break and tensile strength at break.

[0007]

[Means for Solving the Problems] The present inventors have conducted extensive studies to solve the above-mentioned various drawbacks. As a result, PAS produced 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 is High molecular weight PA that gives a sheet-shaped molded product having excellent tensile elongation at break and tensile strength at break by heat treatment at room temperature
The inventors have found that it can be S and completed the present invention.

That is, according to the present invention, an alkali metal sulfide is reacted with a dihaloaromatic compound in an organic amide solvent,
In addition, during the reaction, the gas phase portion of the reaction can is cooled to condense a part of the gas phase in the reaction can, and the polyarylene sulfide (A) produced by refluxing this to the liquid phase is subjected to gas phase oxidation. It is a high molecular weight polyarylene sulfide for a sheet-shaped molded product obtained by heat treatment in a neutral atmosphere.

As a method for producing PAS by cooling a gas phase portion of the reaction can of the present invention to condense a part of the gas phase in the reaction can and refluxing the condensed gas to a liquid phase, JP-A No. 5/1999 can be used.
The method described in JP-A-222196 can be used.

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, 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, at a high temperature of 230 ° C. or higher, when the generated PAS and the raw materials such as Na ₂ S and by-products are uniformly mixed, not only 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 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 the above range, the reaction rate becomes small,
Moreover, the amount of by-products such as phenol increases in the filtrate after the reaction, and the degree of polymerization does not increase. If the amount is less than the above range, 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-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 (A) thus obtained is separated from the by-products by a post-treatment method known to those skilled in the art.

In the present invention, the PAS (A) obtained as described above may be further acid-treated.
The acid treatment is performed at a temperature of 100 ° C. or lower, preferably 40 to 8
It is carried out at a temperature of 0 ° 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-mentioned concentration and pH, -SNa in PAS which is the object to be treated
And -COONa most of the ends are -SH and -COOH
It is preferable because it can be converted to the terminal and corrosion of plant equipment and the like can be prevented. 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. Below the above, -SNa and -COON in PAS
It is not preferable since the a-terminal cannot be sufficiently converted to the -SH and -COOH terminals. 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.

In PAS (A), its melt viscosity V ₆
However, it is preferably 600 poises or more. If the melt viscosity is less than the above value, the PAS molecular weight after the heat-oxidation treatment is too small, and thus the mechanical strength such as tensile rupture elongation and tensile rupture strength of the produced sheet-shaped molded article is not improved, which is not preferable. The melt viscosity V ₆ is a viscosity (poise) measured after holding for 6 minutes at 320 ° C. under a load of 20 kgf / cm ² and L / D = 10 using a flow tester.

Next, PAS (A) is heat-treated in a gas-phase oxidizing atmosphere. The heat treatment can be carried out by a known method. The temperature for the heat treatment is preferably 100 to 280 ° C., particularly preferably 170 to 250.
° C. If the temperature is below the above range, the time required for heat treatment will increase, and if it exceeds the above range, the treated P
It is not preferable because the thermal stability of AS during melting is poor. The time required for the thermal oxidation treatment depends on the above heating temperature or the desired PAS melt viscosity, but is preferably 0.5.
-25 hours, particularly preferably 5-20 hours. If the time is less than the above range, high molecular weight PAS cannot be obtained,
If the amount exceeds the above range, generation of microgels in the treated PAS increases, 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.

The apparatus for performing the heat treatment of the present invention may be a batch type or a continuous type, and a known apparatus can be used. For example, in a closed container equipped with a stirrer, PA
A device for contacting S with an oxygen-containing gas 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.

The high molecular weight PAS for a sheet-shaped molded product produced as described above has a melt viscosity V ₆ of preferably 1,000 to 35,000 poise, particularly preferably 2,000 to 30,000. It's a poise. If the melt viscosity is less than the above range, the tensile elongation at break of the sheet-shaped molded article decreases, and if the melt viscosity exceeds the above range, the extrusion speed at the time of extrusion molding decreases due to the decrease in fluidity, or the sheet-shaped molded article is reduced. It is not preferable because the moldability is deteriorated.

The high molecular weight PAS for a sheet-shaped molded product includes
Conventional additives can be added. 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. Each of these inorganic fillers is
Alternatively, two or more kinds can be used in combination. Further, these inorganic fillers may be treated with a silane coupling agent or a titanate coupling agent. From the viewpoint of melt processability and the like, the blending ratio of the filler is preferably 30% by weight or less in the sheet-shaped molded product. Further, if necessary, an antioxidant, a heat stabilizer, a lubricant, a release agent, and a colorant. It is also possible to add additives such as.

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

The sheet-like molded article produced from the high molecular weight polyarylene sulfide of the present invention preferably has a thickness of 0.02 to 10 mm. By setting the content within the above range, it is possible to obtain a molded product having good tensile elongation at break and tensile strength at break. Further, the sheet-shaped molded product can be generally produced by an inflation method, a T-die method or a press molding method. For example, it is produced by heating and melting a polymer, extruding it from a T-die, rapidly cooling or gradually cooling and winding it.

The sheet-shaped molded product can be used as a sheet and a film for a medical use, a food use, a chemical use, and the like, especially in a high temperature and corrosive environment.

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

[0033]

EXAMPLES In the examples, the melt viscosity V ₆ was 320 using a flow tester CFT-500A manufactured by Shimadzu Corporation.
It is a viscosity (poise) measured after holding for 6 minutes at L / D = 10 at a temperature of 20 kgf / cm ² and a load of 20 kgf / cm ² .

Tensile breaking elongation and tensile breaking strength are AST
It is a value measured according to MD638.

[0035]

Polymerization Example 1 523.1 kg of flaky sodium sulfide (60.8% by weight Na ₂ S) was placed in a 4 m ³ autoclave.
Then, 1200 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) was charged. With stirring under a nitrogen stream, the temperature was raised to 204 ° C., and 126.3 kg of water was distilled off. Then, seal the autoclave 180
After cooling to ℃, p-dichlorobenzene (hereinafter p-D
597.2 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 220
While stirring at 3 ° C. for 3 hours, a cooling medium of 20 ° 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 temperature was stirred at 260 ° C. for 3 hours, the temperature was then 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 8.81 kg / cm ² G
Met.

The resulting slurry was repeatedly filtered and washed with warm water by a conventional method and dried in a hot air circulation dryer at 130 ° C. for about 4 hours to obtain a white powdery intermediate product. The obtained PAS
The melt viscosity V ₆ of (P-01) was 960 poise.

Next, the above intermediate product was charged into a thermal oxidation treatment apparatus of 5 m ³ and stirred at a tank temperature of 220 ° C. for 4 hours.
Then, it cooled and obtained the product. Obtained product (P-1)
The melt viscosity V ₆ thereof was 1,500 poise.

[0038]

Polymerization Example 2 Polymerization Example 1 was repeated except that the thermal oxidation treatment time was 8 hours. Obtained product (P-
The melt viscosity V ₆ of 2) was 3,190 poise.

[0039]

[Polymerization Example 3] Polymerization Example 3 was repeated except that the thermal oxidation treatment time was changed to 15 hours. Obtained product (P-
The melt viscosity V ₆ of 3) was 7,340 poise.

[0040]

Polymerization Example 4 Polymerization Example 4 was repeated except that the thermal oxidation treatment time was 24 hours. Obtained product (P-
The melt viscosity V ₆ of 4) was 33,200 poise.

[0041]

[Comparative Polymerization Example] 523.1 kg of flaky sodium sulfide (60.8 wt% Na ₂ S) and 1200 kg of NMP were charged into a 4 m ³ autoclave. The temperature was raised to 204 ° C. with stirring under a nitrogen stream, and 124.3 kg of water was distilled off. Then, the autoclave was closed and cooled to 180 ° C., and 614.4 kg of p-DCB and 400 kg of NMP were charged. 1 kg / c at a liquid temperature of 150 ° C using nitrogen gas
Pressurization to m ² G was started to raise the temperature. When the liquid temperature reached 255 ° C, the temperature was stopped and the mixture was stirred for 2 hours. Next, the temperature was lowered to 200 ° C. over 1.5 hours. Maximum pressure during reaction is 1
It was 0.31 kg / cm ² G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method and dried in a hot air circulation dryer at 130 ° C. for about 4 hours to obtain a white powdery intermediate product. The obtained PAS
The melt viscosity V ₆ of (P-C01) was 315 poise.

Next, the above intermediate product was placed in a 5 m ³ thermal oxidation treatment apparatus and stirred at a tank temperature of 220 ° C. for 25 hours. Then, it cooled and obtained the product. Obtained product (P-
The melt viscosity V ₆ of C1) was 2,890 poise.

[0044]

[Examples 1 to 4 and Comparative Examples 1 to 3] PASs obtained as described above were treated with a 35 mmφ twin-screw extruder for 32
Melt kneading was performed at a temperature of 0 ° C. to prepare pellets. Furthermore, the obtained pellets are melted at 320 ° C. for 4 minutes by a press molding machine, and then cooled at 130 ° C. for 2 minutes, and 150 m side
A sheet-shaped molded product having a thickness of m and a thickness of 0.2 mm was obtained. The sheet-shaped molded product was punched into a dumbbell mold (ASTM No. 4), and the tensile breaking strength and tensile breaking elongation were measured.

The above results are shown in Table 1.

[0046]

[Table 1] In Example 1, as compared with Comparative Example 1 in which the thermal oxidation treatment was not performed, the tensile rupture elongation and the tensile rupture strength of the molded body were good. In Examples 2 to 4, the thermal oxidation treatment time was made longer than that in Example 1, and the PAS melt viscosity was increased within the range of the present invention. In both cases, the tensile rupture elongation and tensile rupture strength of the molded product were better than those of Example 1. In Comparative Example 2, the gas phase portion of the reaction can was not cooled during the production of PAS. PAS (A) had a remarkably low melt viscosity and could not be molded. In Comparative Example 3, the PAS obtained in Comparative Example 2 was subjected to thermal oxidation treatment, and the tensile rupture elongation and tensile rupture strength of the molded body were significantly lower than those of the Examples.

[0047]

INDUSTRIAL APPLICABILITY The present invention provides an inexpensive high molecular weight polyarylene sulfide which gives a sheet-shaped molded product having excellent tensile elongation at break and tensile strength at break.

Claims (5)

[Claims] 1. A part of a gas phase in a reaction can by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent and cooling the gas phase part of the reaction can during the reaction. Of the polyarylene sulfide (A) produced by condensing the polymer and refluxing it in a liquid phase, and heat-treating the polyarylene sulfide (A) in a gas phase oxidizing atmosphere for a sheet-shaped molded article. 2. A melt viscosity V ₆ of 1,000 to 35,000.
The high molecular weight polyarylene sulfide for a sheet-shaped molded product according to claim 1, which has 0 poise. 3. A melt viscosity V ₆ of 2,000 to 30,000.
The high molecular weight polyarylene sulfide for a sheet-shaped molded product according to claim 1, which has 0 poise. 4. The high molecular weight polyarylene sulfide for a sheet-shaped molded product according to claim 1, wherein the melt viscosity V ₆ of the polyarylene sulfide (A) is 600 poise or more. 5. A sheet-shaped molded product having a thickness of 0.02 to 10 mm, which is produced from the high molecular weight polyarylene sulfide for a sheet-shaped molded product according to any one of claims 1 to 4.