JP2001002920A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition which simultaneously has good high temperature compression creep resistance, good chemical resistance, high weld strength and high flowability. SOLUTION: This polyarylene sulfide resin composition comprises (A) 40 to 95 wt.% of a polyarylene sulfide which has a melt viscosity of 8,000 to 50,000 poises (measured with a flow tester at a measuring temperature of 300 deg.C under a load of 20 kg/cm2 in an L/D of 10/1 for a retention time of 6 minutes), and (B) 60 to 5 wt.% of a polyarylene sulfide which has a melt viscosity of 1,000 to 8,000 poises (measured with a flow tester at a measuring temperature of 300 deg.C under a load of 20 kg/cm2 in an L/D of 10/1 for a retention time of 6 minutes), wherein the ratio of the melt viscosity of the component B to the melt viscosity of the component A is 0.1 to 0.7.

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 a polyarylene sulfide resin composition having excellent insulating properties, sealing properties, weld strength, and toughness.

[0002]

2. Description of the Related Art Polyarylene sulfide such as polyphenylene sulfide (hereinafter sometimes abbreviated as PAS) has excellent mechanical strength, heat resistance, chemical resistance, electrical properties, flame retardancy, and dimensional stability. Due to its physical properties, it has been widely used in recent years for component materials such as automobiles, electric / electronic parts, and chemical equipment. In particular, high molecular weight PAS has been developed with high toughness in addition to heat resistance due to remarkable development of high molecular weight technology, and its industrial applications are expanding.

[0003] By the way, long-term compression creep resistance is required for an electrode insulating sealing material inside a primary battery or a secondary battery, and a polypropylene resin has conventionally been used in many cases. With the recent expansion of applications such as high-voltage, high-energy density lithium-ion batteries and mounting on vehicles such as electric vehicles, and changes in use under high temperatures, the temperature inside the batteries exceeds 100 ° C and reaches 200 ° C. This is not uncommon, and the safety requirements for battery components are becoming more stringent. On the other hand, the conventional polypropylene sealing material is not only difficult to maintain a long-term compression creep property at 100 ° C. or more, but also melts at 200 ° C. or more, cannot maintain the sealing property, and has a liquid leakage. It has been pointed out that it is dangerous.

On the other hand, the thickness of the electrode insulating sealing material inside the primary battery or the secondary battery by injection molding is usually 0.1 to 5 mm.
It is a molded product having a size of about mm and having a welded portion in many cases. Causes of the decrease in the sealing property of the electrode insulating seal material include a decrease in compression creep property due to the temperature of the material or the chemical and a crack in a weld portion. Polyarylene sulfide is expected as a material having chemical resistance other than polypropylene.However, with conventional high-viscosity type high-toughness polyarylene sulfide, thin-wall molding is difficult, or the sealability is inadequate due to cracks in the weld. Easy to occur. PAS / polyphenylene oxide, PAS / polyphenylene ether, PAS / polyphenylene oxide blended with polyarylene sulfide and another thermoplastic resin.
In PAS alloys such as olefin copolymers and PAS / styrene / ethylene butene / styrene copolymer compositions,
There is a problem that chemical resistance and compression creep under high temperature are low, and it is difficult to maintain the sealing property for a long period of time.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyarylene sulfide resin composition having high-temperature compression creep, chemical resistance, high weld strength and high fluidity, and particularly to an electrode insulating sealing material inside a battery. be able to,
An object of the present invention is to provide a polyarylene sulfide resin composition excellent in high-temperature compression creep property and weld strength.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have combined two types of high molecular weight polyarylene sulfides having a specific melt viscosity and adjusted the melt viscosity ratio to a specific range. Thus, the present inventors have found that a polyarylene sulfide resin composition having excellent high-temperature compression creep properties, chemical resistance, insulating sealing properties, and weld strength can be obtained, and the present invention has been completed.

That is, the present invention relates to a melt viscosity (flow tester, measurement temperature 300 ° C., load 20 kg / cm ² , L
/ D = 10/1, retention time 6 minutes) is 8,000-5
40 to 95% by weight of a polyarylene sulfide (A) of 0000 poise, melt viscosity (flow tester, measurement temperature 300 ° C., load 20 kg / cm ² , L / D
= 10/1, retention time 6 minutes) from 1,000 to 8,000
0 poise polyarylene sulfide (B) 60-
A polyarylene sulfide resin composition comprising 5% by weight and having a melt viscosity ratio (B) / (A) of 0.1 to 0.7.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyarylene sulfide resin composition of the present invention comprises two types of high molecular weight polyarylene sulfides, a high melt viscosity polyarylene sulfide and a lower melt viscosity polyarylene sulfide. Are described in detail below.

1. Polyarylene sulfide resin Polyarylene sulfide (PA) used in the present invention
S) is a polymer whose repeating unit substantially consists of -RS- (R: aryl group). Preferably, a polymer having a paraphenylene group as a repeating unit, and a paraphenylene group as a main component and other arylene groups as a minor component, for example, an m-phenylene group, an o-phenylene group, an alkyl-substituted phenylene group,
p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'-diphenylene ether group, p, p
Examples include random copolymers and block copolymers having a p'-diphenylenecarbonyl group, a naphthalene group, and the like. In addition, these polyarylene sulfide resins may be a mixture. A particularly preferred resin is a polyparaphenylene sulfide resin (hereinafter, may be abbreviated as PPS).

[0010] 2. Polyarylene sulfide (A) The polyarylene sulfide (A) used in the polyarylene sulfide resin composition of the present invention needs to have high toughness and high heat resistance, and has a melt viscosity (flow tester, measurement temperature of 300 ° C., load of 20 kg). / Cm ² , L / D = 10 /
1, holding time of 6 minutes) is 8,000 to 50,000 poise, preferably 10,000 to 30,000 poise. If the melt viscosity is less than 8,000 poise, the toughness such as compressive creep properties will decrease, and if it exceeds 50,000 poise, the fluidity during melting will decrease.

[0011] Such a polyarylene sulfide
The production method of (A) includes a substantially linear melting method.
Viscosity (flow tester, measurement temperature 300 ° C, load 20k
g / cm ², L / D = 10/1, retention time 6 minutes) 1,
200 to 3,000 poise, preferably 1,400 to
Thermal cross-linking of 2,500 poise polyarylene sulfide
Melt viscosity (flow tester, measurement temperature 300 ° C, load
Weight 20kg / cm², L / D = 10/1, retention time 6 minutes
Between) 8,000 to 50,000 poise is preferred
New

As a method of the thermal crosslinking, a heat treatment in a gas phase oxidizing atmosphere can be mentioned. The heat treatment can be performed by a known method. For example, the temperature at which the heat treatment is performed is preferably 100 to 280 ° C, particularly preferably 170 to 260 ° C. If the temperature is lower than the above range, the time required for the heat treatment increases, and if the temperature exceeds the above range, the thermal stability of the treated PAS at the time of melting is undesirably reduced. The time required for the heat treatment depends on the heating temperature or the desired melt viscosity of PAS, but is preferably 0.5 to 50 hours, particularly preferably 1 to 50 hours.
30 hours. If the time is less than the above range, a high toughness PAS cannot be obtained, and if the time exceeds the above range, the treated PAS will not be obtained.
The generation of microgel during S 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 a mixture of any of these with an appropriate inert gas. Examples of the inert gas include water vapor, nitrogen, carbon dioxide, and the like, and 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. The oxygen concentration is
Beyond the above range, the amount of generated radicals increases, the viscosity at the time of melting becomes remarkable, and the hue is undesirably dark,
If it is less than the above range, the thermal oxidation rate is undesirably low.

The apparatus for performing the heat treatment may be a batch type or a continuous type. Examples thereof include an apparatus for bringing PAS into contact with an oxygen-containing gas in a closed vessel equipped with a stirrer. A fluidized bed thermal oxidation treatment apparatus provided is used. The use of such a device makes it possible to reduce the temperature distribution in the bath. As a result, thermal oxidation can be promoted, and non-uniformity of the molecular weight can be prevented.

[0015] Melt viscosity (flow tester, measuring temperature 300) as a raw material for producing polyarylene sulfide (A)
C., load: 20 kg / cm ² , L / D = 10/1, holding time: 6 minutes) The polyarylene sulfide having a molecular weight of 1,200 to 3,000 poise has a substantially linear high molecular weight obtained by polymerization. Polyarylene sulfide may be obtained by any polymerization method. For example, Japanese Patent Publication No. 52-12240 discloses a method for producing a high molecular weight polyarylene sulfide in the presence of a metal carboxylate such as sodium acetate and lithium acetate, and the method described in JP-A-61-7332. In a method for producing a PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, the first step comprises 0.5 to 2.4 moles per mole of the alkali metal sulfide. The reaction is carried out at a temperature of 180 to 235 ° C. in the presence of water to reduce the conversion of the dihaloaromatic compound to 5
0-98 mol%, followed by the addition of additional water in the second stage in the presence of 2.5-7.0 mol of water at 245-290 ° C.
For producing a high molecular weight polyarylene sulfide by further continuing the reaction at a temperature of
No. 196, an alkali metal sulfide is reacted with a dihalo aromatic compound in an organic amide solvent, and the gas phase in the reaction vessel is cooled by cooling the gas phase portion of the reaction vessel during the reaction. A method for producing a high molecular weight polyarylene sulfide produced by condensing a part of the mixture and refluxing the resulting liquid phase into a liquid phase, and a method for producing an alkali metal sulfide in an organic amide solvent described in JP-A-10-195197. During the reaction of the dihalo aromatic compound, the gas phase portion of the reactor is cooled,
After the completion of the reaction, a substantially linear melt viscosity of 1,200 to 3, by a method of producing a high molecular weight polyarylene sulfide by adding a specific amount of an alkaline earth metal compound to the reaction solution slurry, or the like. 000 poise polyarylene sulfide can be produced.

[0016] Among these polymerization methods, a method of producing a PAS by cooling a gas phase portion of a reaction vessel to condense a part of a gas phase in the reaction vessel and refluxing it to a liquid phase to produce a PAS is described. Is preferred. For example, a layer having a high water content is formed on the upper portion of the reaction solution by actively cooling the gas phase portion of the reactor and returning a large amount of the reflux liquid rich in water to the upper portion of the liquid phase. As a result, the layer contains a large amount of residual alkali metal sulfide (eg, Na ₂ S), alkali metal halide (eg, NaCl), oligomers, and the like. In a state where the produced PAS and raw materials such as Na ₂ S and by-products are uniformly mixed, depolymerization of the produced PAS also occurs, and by-products of thiophenol are observed. However, by forming a layer having a high water content in the upper portion of the reaction solution, it is considered that factors that hinder the reaction can be truly efficiently eliminated and a high molecular weight PAS can be obtained.

The gas phase portion of the reaction vessel can be cooled by external cooling or internal cooling, and any method can be used as long as it has an effect of increasing the amount of reflux in the vessel. In the case of external cooling, the water / amide solvent mixture condensed on the reaction vessel wall flows into the liquid layer along the reaction vessel wall. Thus, the water-rich mixture accumulates at the top of the liquid phase, keeping the water content relatively high. In the case of internal cooling, the mixture condensed on the cooling surface likewise travels along the cooling device surface or the reactor wall and into the liquid phase. The reaction temperature is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230-275 ° C for constant temperature
The reaction is preferably performed at a temperature of 0.1 to 20 hours.
More preferably, it is 1 to 6 hours at a temperature of 240 to 265 ° C. To obtain a higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. When performing this two-step operation, the first step is preferably performed at a temperature of 195 to 240 ° C. The completion of the first stage is such that the residual ratio of the dihalo aromatic compound in the polymerization reaction system is 1 to 40 mol%,
Further, it is preferable to carry out the reaction at a time when the molecular weight is in the range of 3,000 to 200,000. Thereafter, the temperature was raised, and the reaction at the final stage was carried out at a reaction temperature of 240 to 270 for 1 hour to 1 hour.
It is preferably performed for 0 hours.

Further, dehydration or water addition is performed as 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 0.5 to 2.5 mol, particularly 0.8 to 2.5 mol per mol of alkali metal sulfide.
1.2 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, and a polyarylene sulfide having a sufficient high molecular weight cannot be obtained.

Cooling of the gas phase during the reaction is performed at a constant temperature for 1 hour.
In the case of a step reaction, it is desirable to carry out from the start of the reaction,
The heating is performed at least during the temperature rise of 250 ° C. or less. In a multi-stage reaction, cooling can be performed from the first stage reaction.
It is preferable to carry out the reaction in the middle of raising the temperature 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. Regarding the absolute value of the pressure,
It depends on the stirring state, the amount of water in the system, the molar ratio between the dihalo aromatic compound and 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 organic amide solvent used is a solvent known for PAS polymerization, for example, N-methylpyrrolidone (NMP), N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with NMP being preferred.

Alkali metal sulfides are also known, for example, lithium sulfide, sodium sulfide, potassium sulfide, 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. The dihalo aromatic compound can be selected from, for example, those described in JP-B-45-3368, but is preferably p-dichlorobenzene. Also, if necessary, 1,2,4-trichlorobenzene,
A polyhalo aromatic compound such as 1,3,5-trichlorobenzene can be used in an amount of 5 mol% or less based on the dihalo aromatic compound. As other small additives, a terminal stopper and a monohalo compound as a modifying agent can be used in combination. The PAS thus obtained is separated from by-products by post-treatment methods known to those skilled in the art.

The PAS used as the raw material of the polyarylene sulfide (A) used in the present invention may be an acid-treated PAS. The acid may be either an organic acid or an inorganic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, benzoic acid, phthalic acid, salicylic acid, acrylic acid, crotonic acid, oleic acid, oxalic acid, maleic acid, and fumaric acid. Can be
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid, boric acid, and carbonic acid. In addition, these acid salts can also be used. Of these, acetic acid and hydrochloric acid are preferred. The acid treatment of the PAS may be an acid treatment of the slurry after the completion of the polymerization reaction, or an acid treatment after filtering and purifying the PAS.

When the PAS slurry is subjected to an acid treatment, an acid is added so that the pH of the PAS slurry after the acid treatment becomes 7.0 to 11.0, preferably 7.5 to 10.0. As described above, the amount of the acid added is such that the pH of the PAS slurry is 7.
The amount may be 0 to 11.0, and depends on the type of acid and the pH of the PAS slurry, but is preferably 0.2 to 10 mol%, preferably 1 to 10 mol%, per mol of the charged alkali metal sulfide. 0.5 to 6.0 mol%. If the acid is liquid,
As is or other solvents (eg N-methylpyrrolidone)
And, if it is a solid, dissolve in an appropriate solvent (water, alcohol, N-methylpyrrolidone, etc.) and add. The acid treatment temperature can be any temperature up to the PAS polymerization reaction temperature, but is preferably from room temperature to 250 ° C. The acid treatment time is 5 minutes to 24 hours, preferably 20 minutes.
Minutes to 3 hours.

When the acid treatment is carried out after filtering and purifying the PAS, the PAS is separated and purified by a conventional method,
Treat in the following acid solution: As the solvent, water or water and a small amount of a water-miscible organic solvent can be used. The concentration of the acid solution is 0.01 to 5% by weight,
H is preferably 4-5. The temperature of the treatment with the acid solution is 100 ° C or lower, preferably 40 to 80 ° C. The processing time is 5 minutes to 2 hours, preferably 10 minutes to 1 hour.

3. Polyarylene sulfide (B) The polyarylene sulfide (B) of the present invention has a melt viscosity (flow tester, measurement temperature 300 ° C, load 20 kg /
cm ² , L / D = 10/1, retention time 6 minutes) is 1,0
00 to 8,000 poise, preferably 2,000 to 6,
000 poise. If the melt viscosity is less than 1,000 poise, the toughness such as compression creep property is reduced, and if it exceeds 8,000 poise, the fluidity during melting is reduced.

As such a polyarylene sulfide (B), any PAS can be used as long as the melt viscosity is within this range. Preferably, a PAS having a substantially linear molecular structure is used.

4. Composition ratio and melt viscosity ratio of polyarylene sulfide (A) and polyarylene sulfide (B) The composition ratio of polyarylene sulfide (A) and polyarylene sulfide (B) in the polyarylene sulfide resin composition of the present invention is as follows. Sulfide (A)
Is 40 to 95% by weight, preferably 50 to 80% by weight, and the polyarylene sulfide (B) is 60 to 5% by weight, preferably 50 to 20% by weight. If the polyarylene sulfide (A) is less than 40% by weight (the polyarylene sulfide (B) exceeds 60% by weight), the toughness and weld strength are not sufficient, and the polyarylene sulfide (A) exceeds 95% by weight (poly When the arylene sulfide (B) is less than 5% by weight), the fluidity at the time of melting is reduced. Further, the melt viscosity ratio (B) / (A) of polyarylene sulfide (A) and polyarylene sulfide (B)
Is 0.1 to 0.7, preferably 0.2 to 0.6. If the melt viscosity ratio is less than 0.1 and exceeds 0.7, sufficient toughness and weld strength cannot be obtained.

5. Other Components A silane compound can be added to the polyarylene sulfide resin composition of the present invention in order to further improve fluidity and weld strength. As the silane compound,
Examples include polysiloxane and silane coupling agents. Examples of the polysiloxane include modified and / or unmodified polyorganosiloxanes. Specific examples include unmodified polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polydimethyl-diphenylsiloxane. Modified polyorganosiloxane partially modified with a functional group such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a methacryloxy group, and a mercapto group is exemplified. The viscosity of the polysiloxane is from 100 to 500,000 centistokes, preferably from 1,000 to 100,000 centistokes. Examples of the silane coupling agent include an alkoxysilane having an amino group, an epoxy group, a methacryloxy group, a mercapto group, a vinyl group, a ureide group, and the like. Specifically, γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, vinyltriethoxysilane and the like. These silane compounds can be used alone or in combination of two or more. In the present invention, the total of polyarylene sulfide (A) and polyarylene sulfide (B) is 10
The silane compound may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 0 parts by weight.

Further, in order to obtain a molded product excellent in performance such as mechanical strength, heat resistance, dimensional stability, and electrical properties,
If necessary, an inorganic filler can be blended. As the inorganic filler, known fillers such as fibrous, powdery and plate-like fillers are used. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and stainless steel. Inorganic fibrous materials such as fibrous materials of metals such as aluminum, titanium, copper, and brass can be used. Particularly typical fibrous fillers are glass fibers and carbon fibers. Also, polyamide, fluororesin,
Substances from high-melting organic fibrous substances such as polyester resins and acrylic resins, and thermosetting resins such as epoxy resins and phenol resins can also be used. Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, silicates such as calcium silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite, and iron chloride. Metal oxides such as titanium oxide, zinc oxide, alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, hydrotalcite, lithium aluminum composite hydroxide Composite metal salt compounds such as chlorides, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. Whiskers such as potassium titanate, potassium borate, and aluminum borate can also be used. These inorganic fillers can be used alone or in combination of two or more.
The combination of fibrous fillers, especially glass or carbon fibers, with particulate and / or plate-like fillers is a particularly preferred combination.

The amount of the inorganic filler used is preferably 400 parts by weight or less, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin composition. If the amount exceeds 400 parts by weight, the molding operation becomes difficult, which is not preferable.

In using the above-mentioned inorganic filler, it is preferable to use a sizing agent such as a silane coupling agent or a titanate coupling agent or a surface treatment agent, if necessary. These may be used when the inorganic filler is subjected to surface treatment or convergence treatment in advance, or may be added at the same time when the composition is prepared.

Further, the polyarylene sulfide resin composition of the present invention may contain known substances generally added to thermoplastic resins and thermosetting resins, for example, stabilizers such as antioxidants and ultraviolet absorbers, and antistatic agents. , A flame retardant, a coloring agent such as a dye or a pigment, a lubricant, a crystallization accelerator, and the like can be appropriately added as necessary. In particular, in the present invention, PAS (A) and P
The melt viscosity ratio of AS (B) is an important factor, and in order to avoid a remarkable viscosity change due to heat history, Irganox 1
It is desirable to add an antioxidant such as 010 to the total of 100 parts by weight of PAS (A) and PAS (B) in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight.

5. Preparation of Composition The preparation of the polyarylene sulfide resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. That is, the method of mixing the necessary components is a method in which each component is dry-blended using a Henschel mixer or the like in advance, kneaded using a single-screw or twin-screw extruder, and extruded to form pellets for molding, a method of forming the required components. A method of mixing and molding a part as a master batch, a method of dissolving necessary components in a solution at the time of PAS synthesis so as to have a predetermined amount, and the like may be used.

6. Applications The polyarylene sulfide resin composition of the present invention is a resin composition having high-temperature compression creep properties, chemical resistance, weld strength, and moldability, and is used in automobiles, electric / electronic parts,
It can be used as a component material for chemical equipment and the like, and in particular, it can be used as an electrode insulating sealing material inside a primary or secondary battery or a gas sealing material such as high-temperature corrosive.

[0035]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not particularly limited to the examples. In addition, the test method in an Example is as follows. (1) Melt viscosity: Flow tester CFT- manufactured by Shimadzu Corporation
Using 500C, measurement temperature 300 ° C, load 20kg / cm
^2. Measured after holding at L / D = 10/1 for 6 minutes. (2) Fluidity evaluation: SG-150S manufactured by Sumitomo Heavy Industries, Ltd.
Using YCAPIII type, width 5mm x filling direction length 5
An injection-molded test piece having a size of 0 mm x a thickness of 0.3 mm was molded, and the state of filling the test piece was determined according to the following criteria. ：: Good filling △: Partially poor filling ×: Poor filling (3) Spring back: Shimadzu AG-5000
Using B, make an injection test piece of 5mm width × 5mm length × 6mm thickness, compress the test piece until the thickness becomes 1/2, and measure the ratio of the height after unloading to the height before loading. These values were obtained, and the compression and unloading conditions were as follows. Unloading after room temperature, 50% strain, 1 second: Compressed at a test speed of 1 mm / min in a constant temperature room at 23 ° C., compressed to 50%,
Unload immediately. 100 ° C., 50% strain, unloading after 7 days: Compressed at a test speed of 1 mm / min in a 100 ° C. chamber, 50%
Uncompressed after holding for 7 days.

(4) Number of breaks in weld: A made by Shimadzu Corporation
Using G-5000B, a tensile test (ASTM D63
8) was performed. However, the test piece was filled with molten resin from the grips at both ends, and the ASTM Type was adjusted and formed so that the flow collided at the center parallel portion (weld portion).
e-1 compliant one was used. (5) Tensile strength: measured using Shimadzu AG-5000B in accordance with ASTM-D638. The tensile speed was 5 mm / min, the distance between the chucks was 115 mm, and the test piece was based on ASTM Type-1. (6) Weld tensile strength: SG-15 manufactured by Sumitomo Heavy Industries, Ltd.
ASTM Type-1 compliant (thickness 3.2) prepared using OSYCAPIII type and filled from the grips at both ends of the test piece and prepared so that the flow hits (weld) at the parallel center.
mm), the following holding pressure and strength were measured. Lower limit holding pressure: The lowest pressure that can be filled up to the weld portion Lower limit holding pressure strength: Tensile strength of a test piece obtained by molding with the lowest filling pressure that can be filled Holding pressure: 468 kg / cm ² hours Strength: Holding pressure 468kgf /
Tensile strength of a test piece obtained by molding in cm ^{2 The} lower limit holding pressure is a value obtained by multiplying the indicated pressure (gauge pressure) of the molding machine by the projected area.

Synthesis Example In a 150-liter autoclave, 15.400 kg of flaky sodium sulfide (60.81% by weight Na ₂ S) was added.
38.0 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) was charged. The temperature was raised to 216 ° C. while stirring under a nitrogen stream, and 3.843 kg of water was distilled off. After that, the autoclave is sealed and
Then, 17.587 kg of p-dichlorobenzene, 0.057 kg of calcium acetate (0.3 mol% based on 1 mol of sodium sulfide charged) and 16.0 kg of NMP were charged. 1 kg / cm ² using nitrogen gas at a liquid temperature of 150 ° C.
G was applied to start heating. The solution was heated with stirring over 2 hours to a liquid temperature of 220 ° C., and kept at this temperature for 4 hours. Thereafter, the temperature was raised again and the temperature was raised to a liquid temperature of 260 ° C. over 2 hours. When the liquid temperature reached 260 ° C., water was sprayed on the upper part of the autoclave, and the temperature was maintained for 4 hours to proceed the reaction. 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. The maximum pressure during the reaction was 8.72 kg /
cm ² G. The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried with hot air at 120 ° C. for about 8 hours to obtain a white powdery product. The melt viscosity of the obtained PPS was 1620 poise. The PPS obtained above was subjected to a thermal oxidation treatment in an air atmosphere using a hot-air circulation oven set at 230 ° C. Table 1 shows the melt viscosity of the obtained PPS and the time spent for the thermal oxidation treatment.

[0038]

[Table 1]

Example 1 PPS having a melt viscosity of 8,120 poise and PPS having a melt viscosity of 2,410 poise obtained in the synthesis example were blended in the ratio shown in Table 2 and preliminarily mixed for 5 minutes using a Henschel mixer. After homogenization, the mixture was melt-kneaded at a temperature of 300 ° C. and a rotation speed of 250 rpm using a 25 mmφ twin-screw rotary extruder to form pellets. The obtained pellet was supplied to an injection molding machine to prepare a test piece, and the physical properties were evaluated. Table 2 shows the results.
Shown in

Examples 2 to 8 The PPS of each melt viscosity obtained in the synthesis examples was designated as PPS (A).
PPS (B) shown in Tables 2 and 3 were blended, and a test piece of the PPS composition was obtained in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Tables 2 and 3.

Examples 9 to 11 PPS (A), PPS (B) and silane compounds obtained in the synthesis examples were blended in the proportions shown in Table 3, and P
A test piece of the PS composition was obtained, and its physical properties were evaluated. Table 3 shows the results.

[0042]

[Table 2]

[0043]

[Table 3]

Comparative Example 1 Melt viscosity of 12,530 obtained in Synthesis Example as PPS (A)
A PPS test piece was obtained in the same manner as in Example 1 except that poise PPS was used and PPS (B) was not used, and the physical properties were evaluated. Table 4 shows the results.

Comparative Examples 2-3 Melt viscosity of 12,530 obtained in the synthesis example as PPS (A)
A test piece of a PPS composition was obtained in the same manner as in Example 9 except that poison PPS was used, PPS (B) was not used, and the amount of the silane compound used was as shown in Table 4, and the physical properties were evaluated. did. Table 4 shows the results.

Comparative Example 4 A test piece of PPS was obtained in the same manner as in Example 1 except that PPS (A) was not used, and its physical properties were evaluated. Table 4 shows the results.

Comparative Examples 5 to 10 Test pieces of the PPS composition were obtained in the same manner as in Example 1 except that PPS shown in Tables 4 and 5 were used and blended in the proportions shown in Tables 4 and 5. Physical properties were evaluated. The results are shown in Tables 4 and 5.

[0048]

[Table 4]

[0049]

[Table 5]

As is clear from Tables 2 and 3, the P
The PS composition is excellent in fluidity and excellent in springback property indicating compression creep property, and particularly excellent in high temperature compression creep property from the value of springback under high temperature. Also,
In the weld number break number test, the number of breaks is small,
Excellent weld tensile strength and holding pressure. Meanwhile, Table 4
As is clear from ~ 5, if PPS (B) is not used,
The fluidity is reduced, and the strength of the weld is reduced (Comparative Examples 1 to 5).
3) However, when PPS (A) is not used, the springback value at high temperatures decreases, and the number of breaks at the weld portion increases (Comparative Example 4). Further, the melt viscosity of PPS (B) is 1,0.
When the melt viscosity ratio of PPS (A) to PPS (B) is less than 0.1 or less than 0.1 poise, the springback value at high temperature decreases, and the fracture at the weld portion increases (Comparative Example 5). Further, when the mixing ratio of PPS (A) and PPS (B) is out of the range of the present invention, the number of breaks at the weld portion increases and the fluidity decreases (Comparative Examples 6, 7, and 8). P
The melt viscosity range of PS (A) and PPS (B) exceeds the range of 0.7 of the present invention, or the melt viscosity of PPS (A) is 8,
When it is smaller than 000 poise, the springback value at a high temperature decreases and the number of breaks in the weld portion increases (Comparative Examples 9 and 10).

[0051]

As described in detail above, the polyarylene sulfide resin composition of the present invention comprising two kinds of polyarylene sulfides has been required for a long time to meet the requirements for high-temperature compression creep property, chemical resistance and weld strength. It has the necessary and sufficient injection moldability, is excellent in weld strength, shows no breakage of weld in molding and shows base material breakage, automobile, electric / electronic parts, chemical equipment And the like, and in particular, it can be used as an electrode insulating sealing material inside a primary or secondary battery.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) (C08L 81/02 83:04) F term (reference) 4J002 CN01W CN01X CP033 CP053 CP093 CP103 EX016 EX036 EX066 EX076 EX086 FD010 FD146 GQ01 5H011 AA02 AA03 AA17 GG01 HH02 HH11 KK02 KK04 KK06 5H022 AA09 CC01 CC11 CC21 EE06 EE10 KK03 KK07

Claims (4)

[Claims] 1. Melt viscosity (flow tester, measurement temperature 3
40 ° C., load 20 kg / cm ² , L / D = 10/1, holding time 6 minutes) 40-95% by weight of polyarylene sulfide (A) having 8,000-50,000 poise.
And a polyarylene sulfide (B) 60 having a melt viscosity (flow tester, measurement temperature 300 ° C., load 20 kg / cm ² , L / D = 10/1, holding time 6 minutes) of 1,000 to 8,000 poise. And a melt viscosity ratio of (B) / (A) of 0.1 to 0.7, which is a polyarylene sulfide resin composition. 2. Polyarylene sulfide (A) has a melt viscosity (flow tester, measurement temperature 300 ° C., load 20 k
g / cm ² , L / D = 10/1, retention time 6 minutes) 1,
The polyarylene sulfide resin composition according to claim 1, which is a polyarylene sulfide having a melt viscosity of 8,000 to 50,000 poise by thermally crosslinking a polyarylene sulfide having 200 to 3,000 poise. 3. The polyarylene sulfide resin according to claim 1, comprising 0.1 to 5 parts by weight of a silane compound based on 100 parts by weight of the total of the polyarylene sulfide (A) and the polyarylene sulfide (B). Composition. 4. An electrode insulating sealing material for a lithium battery or the like, comprising the polyarylene sulfide resin composition according to claim 1.