JP2021004351A - Polyphenylene sulfide resin composition, and insulation member and gasket for primary or secondary battery comprising the same - Google Patents

Abstract

To obtain a polyphenylene sulfide resin composition excellent in tracking resistance, and toughness.SOLUTION: The polyphenylene sulfide resin composition is obtained by compounding (a) a polyphenylene sulfide resin, (b) a molten fluororesin, and (c) an olefin resin, where when a total of constituent (a), constituent (b), and constituent (c) is 100 vol.%, a total of constituent (a). and constituent (c) is 1 vol.% or more and 68 vol.% or less, and constituent (b) is 32 vol.% or more and 99 vol.% or less, and in a tracking resistance test (IEC60112) of a test specimen obtained by injection-molding the resin composition, the tracking resistance is rank 0.SELECTED DRAWING: None

Description

The present invention relates to a polyphenylene sulfide resin composition having excellent tracking resistance and toughness, and an insulating member and gasket for a primary or secondary battery comprising the polyphenylene sulfide resin composition.

Polyphenylene sulfide (hereinafter abbreviated as "PPS") resin is an engineering plastic having excellent heat resistance, flame retardancy, chemical resistance, electrical insulation, moisture heat resistance, mechanical strength, dimensional stability, and the like.

Since the PPS resin can be molded by various molding methods such as injection molding and extrusion molding, it is put into practical use in a wide range of fields such as electric / electronic parts, mechanical parts and automobile parts. Further, in recent years, PPS resin has been widely used as a constituent member of a primary or secondary battery used in electric vehicles, communication devices, etc., which are required to have heat resistance and chemical resistance.

However, among the electrical characteristics, the tracking resistance of the PPS resin has a drawback that it is inferior to other engineering plastics such as polyamide resin and polyester resin.

Therefore, attempts have been made to improve the tracking resistance of the PPS resin, and a method of adding magnesium hydroxide to the PPS resin is known.

For example, Patent Document 1 describes a method of improving tracking resistance by adding magnesium hydroxide to a PPS resin.

On the other hand, it has been proposed to improve the tracking resistance of the PPS resin by adding another resin to the PPS resin in addition to magnesium hydroxide.

For example, fluororesin has lower strength than PPS resin, but has excellent chemical resistance, weather resistance, non-adhesiveness, releasability, slidability, and high tracking resistance. Similarly, the olefin resin also has excellent tracking resistance, although it is inferior in heat resistance and strength to the PPS resin. By blending such a fluororesin or an olefin resin with magnesium hydroxide into a PPS resin, it has been proposed to develop tracking resistance that is difficult to achieve by itself.

Patent Document 2 describes a composition obtained by adding magnesium hydroxide, a polyolefin-based polymer and / or a polyolefin-based copolymer, silicone, and a fluororesin to a PPS resin.

On the other hand, the compatibility between the PPS resin and the fluororesin is low, and even if they are mixed, the characteristics are not necessarily improved. On the other hand, in Patent Document 3, the ethylene-tetrafluoroethylene copolymer and the PPS resin can be obtained by adding an ethylene-tetrafluoroethylene copolymer having a low melting point and a high melt viscosity and a compatibilizer to the PPS resin. An application has been filed to obtain a polymer alloy that is microdispersed and has good mechanical properties.

Further, in Patent Document 4, the fluororesin is dispersed in the PPS resin phase by a method of melt-kneading two or more components of the fluororesin and then kneading the fluororesin with the PPS resin at a temperature equal to or lower than the melting point of the fluororesin of one component. By forming a phase and further dispersing the fluororesin component that was not melted during kneading in the dispersed phase in a core-shell shape, the compatibility between the PPS resin and the fluororesin of two or more components is improved, and various physical properties and appearance. Inventions for improving the above are described.

Japanese Unexamined Patent Publication No. 5-271542 Japanese Unexamined Patent Publication No. 8-291253 International Publication No. 1998/21277 Japanese Unexamined Patent Publication No. 3-263464

However, in the invention described in Patent Document 1, although a PPS resin composition having excellent tracking resistance is obtained, sufficient toughness cannot be imparted because magnesium hydroxide is blended.

Similarly, in Patent Document 2, a PPS resin composition having excellent tracking resistance is obtained by blending a polyolefin-based polymer and / or a polyolefin-based copolymer, silicone, and a fluororesin, but magnesium hydroxide. Because it contains, sufficient toughness cannot be imparted.

On the other hand, the resin compositions described in Patent Documents 3 and 4 are resin compositions composed of PPS resin and fluororesin without containing an inorganic filler, but the resin compositions having the disclosed compositions are sufficient. Tracking resistance cannot be added.

An object of the present invention is to obtain a polyphenylene sulfide resin composition having excellent tracking resistance and toughness while maintaining the heat resistance and chemical resistance inherent in a PPS resin, and further, a primary or a primary using the resin composition or An object of the present invention is to provide an insulating member and a gasket for a secondary battery.

As a result of diligent studies to solve such a problem, the present invention controls the volume composition of each component to a specific ratio in a resin composition containing a PPS resin, a molten fluororesin and an olefin resin as essential components. Therefore, a polyphenylene sulfide resin composition having excellent tracking resistance and toughness is obtained. Further, as an insulating member or gasket used for a primary or secondary battery, it is possible to provide a member having excellent heat resistance, chemical resistance, tracking resistance and toughness.

That is, the present invention has been made to solve at least a part of the above-mentioned problems, and can be implemented as the following embodiments.
A resin composition comprising (1) (a) a polyphenylene sulfide resin, (b) a molten fluororesin, and (c) an olefin resin, which comprises the components (a), (b), and (c). A polyphenylene sulfide resin composition in which the total of the components (a) and (c) is 1% by volume or more and 68% by volume or less, and the component (b) is 32% by volume or more and 99% by volume or less, assuming that the total is 100% by volume. A polyphenylene sulfide resin composition having rank 0 tracking resistance in a tracking resistance test (IEC60112) of a test piece obtained by injection molding the resin composition.
(2) In the tensile test (ISO527-1 and 2) of the test piece of the polyphenylene sulfide resin composition according to (1) obtained by injection molding the resin composition, a tensile breaking strain of 5% or more was obtained. Polyphenylene sulfide resin composition having.
(3) The polyphenylene sulfide resin composition according to any one of (1) to (2), wherein the component (c) is a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid anhydride group, and the like. A polyphenylene sulfide resin composition which is an olefin resin having at least one functional group selected from the isocyanate group.
(4) The polyphenylene sulfide resin composition according to any one of (1) to (3), wherein the component (c) is an olefin elastomer.
(5) The polyphenylene sulfide resin composition according to any one of (1) to (4), wherein the component (b) is a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid anhydride group, and the like. A polyphenylene sulfide resin composition which is a molten fluororesin having at least one functional group selected from the isocyanate group.
(6) The polyphenylene sulfide resin composition according to any one of (1) to (5), wherein the component (b) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer or hexafluoropropylene-. A polyphenylene sulfide resin composition which is at least one molten fluororesin selected from a tetrafluoroethylene copolymer and an ethylene-tetrafluoroethylene copolymer.
(7) An insulating member for a primary or secondary battery made of the polyphenylene sulfide resin composition according to any one of (1) to (6).
(8) A gasket for a primary or secondary battery made of the polyphenylene sulfide resin composition according to any one of (1) to (6).
(9) The method for producing a polyphenylene sulfide resin composition according to any one of (1) to (6), wherein (a) the polyphenylene sulfide resin and (c) the olefin resin are mixed in advance and premixed. A method for producing a polyphenylene sulfide resin composition, which comprises supplying the remaining (b) molten fluororesin separately to an extruder as a product.

According to the present invention, in a PPS resin composition containing a PPS resin, a molten fluororesin, and an olefin resin, by controlling the volume composition of each component to a specific ratio, the tracking resistance CTI rank 0 and the toughness are excellent. A polyphenylene sulfide resin composition can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.

The present invention is a resin composition comprising (a) a polyphenylene sulfide resin, (b) a molten fluororesin, and (c) an olefin resin, wherein the component (a), the component (b), and the component (c) are blended. In a polyphenylene sulfide resin composition in which the total of the components (a) and (c) is 1% by volume or more and 68% by volume or less, and the component (b) is 32% by volume or more and 99% by volume or less. Therefore, it is a polyphenylene sulfide resin composition having rank 0 tracking resistance in a tracking resistance test (IEC60112) of a test piece obtained by injection molding the resin composition. The PPS resin composition of the present invention also includes a reaction product in which the component (a), the component (b), and the component (c) react with each other, and the reaction product is produced by a complicated reaction. There are circumstances in which it is impractical to specify the structure. Therefore, the present invention specifies the invention by the components to be blended.

(1) (a) Polyphenylene sulfide resin The (a) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula.

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the polymer containing the repeating unit represented by the above structural formula is preferable. Further, (a) less than 30 mol% of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure or the like.

Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

On the other hand, if about 30 mol% or more has the above structure, it leads to a decrease in chemical resistance, which is an inherent characteristic of PPS resin, and a decrease in chemical resistance to an electrolytic solution used in a primary battery or a secondary battery. Therefore, it is not preferable.

The weight average molecular weight of the (a) PPS resin used in the present invention is not particularly limited, but the weight average molecular weight is preferably 30,000 to 150,000, more preferably 40,000 to 130,000, and 45,000 to 110,000 from the viewpoint of obtaining more excellent toughness. More preferably, 50,000 to 90,000 is more preferable. When the weight average molecular weight is small, the toughness of the PPS resin itself decreases, so 30,000 or more is preferable. On the other hand, when the weight average molecular weight exceeds 150,000, the melt viscosity becomes remarkably large, which is not preferable in the molding process.

The weight average molecular weight in the present invention is a value calculated in terms of polystyrene using gel permeation chromatography (GPC) manufactured by Senshu Kagaku.

The method for producing the (a) PPS resin used in the present invention will be described below, but the method is not limited to the following method as long as the (a) PPS resin having the above structure can be obtained.

First, the contents of the polyhalogenated aromatic compound, the sulfidizing agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
The polyhalogenated aromatic compound is a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexa. Polyhalogenated aromatics such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene. Group compounds are mentioned, and p-dichlorobenzene is preferably used. Further, for the purpose of introducing a carboxyl group, a carboxyl group-containing dihalogenated aromatic such as 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, and 3,5-dichlorobenzoic acid. It is also one of the preferred embodiments that the compound and a mixture thereof are used as a copolymerization monomer. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but it is preferable that the p-dihalogenated aromatic compound is the main component.

The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1. per mol of the sulfidizing agent, from the viewpoint of obtaining the (a) PPS resin having a viscosity suitable for processing. The range of 5 mol, more preferably 1.005 to 1.2 mol, can be exemplified.

[Sulfide agent]
Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfides.

Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

Further, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Further, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and this can be transferred to a polymerization tank for use.

Alternatively, alkali metal sulfides prepared in situ in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used. Further, an alkali metal sulfide can be prepared from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide, and the alkali metal sulfide can be transferred to a polymerization tank for use.

The amount of the charged sulfidating agent means the residual amount obtained by subtracting the lost amount from the actual charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to a dehydration operation or the like.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfide agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth. Specific examples of the metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.

When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. per 1 mol of alkali metal hydrosulfide. An example is in the range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol.

[Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidi. Examples thereof include aprotic organic solvents typified by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfocide, and mixtures thereof, all of which are used. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.

The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, and more preferably 2.5 to 5.5 mol, per 1 mol of the sulfidizing agent.

[Molecular weight regulator]
(A) A monohalogen compound (not necessarily an aromatic compound) is combined with the above-mentioned polyhalogenated aromatic compound in order to form the terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. Can be used together.

[Polymerization aid]
It is also one of the preferable embodiments to use a polymerization aid in order to obtain the (a) PPS resin having a relatively high degree of polymerization in a shorter time. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained (a) PPS resin. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline soils. Examples include metal phosphates. These can be used alone or in combination of two or more. Of these, organic carboxylate, water, and alkali metal chloride are preferable, alkali metal carboxylate is preferable as the organic carboxylate, and lithium chloride is preferable as the alkali metal chloride.

The alkali metal carboxylate is a general formula R (COMM) _n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. N is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and mixtures thereof. Can be mentioned.

The alkali metal carboxylate is a reaction in which an organic acid and one or more compounds selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate are added in approximately equal chemical equivalents. It may be formed by. Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a polymerization system, is most preferably used.

When these alkali metal carboxylates are used as polymerization aids, the amount used is usually in the range of 0.01 mol to 2 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, The range of 0.1 to 0.6 mol is preferable, and the range of 0.2 to 0.5 mol is more preferable.

When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and is 0.6 to 0.6 in the sense of obtaining a higher degree of polymerization. The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

Of course, two or more of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight in a smaller amount of each.

The timing of addition of these polymerization aids is not particularly specified, and may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times. When an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the same time as the start of the previous step or the start of polymerization because it is easy to add. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the middle of the polymerization reaction after charging it.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses unwanted side reactions. One guideline for the side reaction is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is one of the polymerization stabilizers. Further, when an alkali metal hydrosulfide is used as the sulfide agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water that is excessive with respect to the sulfide agent. Oxides can also be polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more. The ratio of the polymerization stabilizer to 1 mol of the charged alkali metal sulfide is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, and more preferably 0.04 to 0.09 mol. It is preferable to use in. If this ratio is small, the stabilizing effect is insufficient, and if it is too large, it tends to be economically disadvantageous or the polymer yield tends to decrease.

The timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable because it is easy to add at the same time at the start of the process or the start of polymerization.

Next, a preferable method for producing the (a) PPS resin used in the present invention will be specifically described step by step in the order of a pre-step, a polymerization reaction step, a recovery step, and a post-treatment step, but of course, it is limited to this method. It's not something.

[pre-process]
(A) In the method for producing a PPS resin, a sulfidizing agent is usually used in the form of a hydrate, but before adding a polyhalogenated aromatic compound, a mixture containing an organic polar solvent and a sulfidizing agent is raised. It is preferred to warm and remove excess water out of the system.

Further, as described above, as the sulfidizing agent, a sulfidizing agent prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. Can be done. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C. in an inert gas atmosphere. In addition, there is a method in which the temperature is raised to at least 150 ° C. or higher, preferably 180 to 260 ° C. under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. Further, in order to promote the distilling of water, toluene or the like may be added to carry out the reaction.

The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 mol per 1 mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.

[Polymerization reaction step]
(A) PPS resin is produced by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

When starting the polymerization reaction step, the organic polar solvent, the sulfidizing agent and the polyhalogenated aromatic compound are mixed in a temperature range of preferably room temperature to 240 ° C., preferably 100 to 230 ° C. in an inert gas atmosphere. .. A polymerization aid may be added at this stage. The order in which these raw materials are charged may be random or simultaneous.

Such a mixture is usually heated to the range of 200 ° C to 290 ° C. The rate of temperature rise is not particularly limited, but a rate of 0.01 to 5 ° C./min is usually selected, and a range of 0.1 to 3 ° C./min is more preferable.

In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours.

A method of reacting at 200 ° C. to 260 ° C. for a certain period of time before reaching the final temperature and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 260 ° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 to 10 hours.

In order to obtain a polymer having a higher degree of polymerization, it may be effective to carry out the polymerization in a plurality of steps. When the polymerization is carried out in a plurality of steps, it is effective that the conversion rate of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (abbreviated as PHA here) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When a polyhalogenated aromatic compound is excessively added to an alkali metal sulfide in a molar ratio, conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)) -PHA excess (mol)]
(B) In cases other than the above (A) Conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)].

[Recovery process]
(A) In the method for producing a PPS resin, after completion of polymerization, a solid substance is recovered from a polymerization reaction product containing a polymer, a solvent and the like. As the recovery method, any known method may be adopted.

For example, a method of slowly cooling after completion of the polymerization reaction to recover the particulate polymer may be used. The slow cooling rate at this time is not particularly limited, but is usually about 0.1 ° C./min to 3 ° C./min. It is not necessary to slowly cool at the same rate in all the slow cooling steps, and a method of slowly cooling at 0.1 to 1 ° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1 ° C./min or more is used. It may be adopted.

Further, it is also preferable to carry out the above recovery under quenching conditions, and a flash method is mentioned as a preferable method of this recovery method. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in powder form at the same time as the solvent is recovered. It is a method, and the term “flash” as used herein means that a polymerization reaction product is ejected from a nozzle. Specific examples of the flashing atmosphere include nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.

[Post-treatment process]
(A) The PPS resin may be produced through the above polymerization and recovery steps, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, and alkali metal or alkaline earth metal treatment.

When performing acid treatment, it is as follows. The acid used for the acid treatment of (a) PPS resin is not particularly limited as long as it does not have the action of decomposing (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Of these, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate (a) PPS resin such as nitric acid are not preferable.

The acid treatment method includes a method of immersing the (a) PPS resin in an acid or an aqueous solution of an acid, and if necessary, stirring or heating can be performed as appropriate. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous solution of pH 4 heated to 80 to 200 ° C. and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, pH 4 to 8. The acid-treated (a) PPS resin is preferably washed with water or warm water several times in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of (a) preferable chemical modification of the PPS resin by the acid treatment is not impaired.

When hot water treatment is performed, it is as follows. (A) When treating the PPS resin with hot water, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If the temperature is lower than 100 ° C., the effect of (a) preferable chemical modification of the PPS resin is small, which is not preferable.

The water used is preferably distilled water or deionized water in order to exhibit the effect of (a) preferable chemical modification of the PPS resin by hot water washing. There is no particular limitation on the operation of hot water treatment, and a method of adding a predetermined amount of (a) PPS resin to a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, etc. Be told. The ratio of (a) PPS resin to water is preferably large in water, but usually, a bath ratio of (a) 200 g or less of PPS resin is selected with respect to 1 liter of water.

Further, since the decomposition of the terminal group is not preferable in the treatment atmosphere, it is desirable to set the treatment atmosphere in an inert atmosphere in order to avoid this. Further, the (a) PPS resin that has been subjected to this hot water treatment operation is preferably washed with warm water several times in order to remove residual components.

When cleaning with an organic solvent, it is as follows. The organic solvent used for cleaning the (a) PPS resin is not particularly limited as long as it does not have the action of decomposing the (a) PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc. Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphorasamide, and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone, and sulfolane, and ketones such as acetone, methylethylketone, diethylketone, and acetophenone. Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene, etc. Alcohol-phenolic solvents such as halogen-based solvents, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and aromatic hydrocarbon-based solvents such as benzene, toluene and xylene. Examples include solvents. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. Moreover, these organic solvents are used in one kind or a mixture of two or more kinds.

As a method of cleaning with an organic solvent, there is a method such as immersing the (a) PPS resin in the organic solvent, and it is also possible to appropriately stir or heat if necessary. The cleaning temperature when cleaning the (a) PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature higher than the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect is usually obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.

Examples of the method for treating alkali metal and alkaline earth metal include a method of adding an alkali metal salt and an alkaline earth metal salt before, during, and after the above-mentioned pre-step, before the polymerization step, during the polymerization step, and after the polymerization step. Later, a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization kettle, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle, or last stages of the above-mentioned cleaning step can be mentioned. Among them, the easiest method includes a method of adding an alkali metal salt and an alkaline earth metal salt after removing residual oligomers and salts by washing with an organic solvent or washing with warm water or hot water. The alkali metal and alkaline earth metal are preferably introduced into PPS in the form of alkali metal ions such as acetates, hydroxides and carbonates, and alkaline earth metal ions. Further, it is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water or the like. The alkali metal ion and alkaline earth metal ion concentrations at the time of introducing the alkali metal and alkaline earth metal are preferably 0.001 mmol or more, more preferably 0.01 mmol or more with respect to 1 g of PPS. The temperature is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, and particularly preferably 90 ° C. or higher. Although there is no particular upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (weight of the cleaning liquid with respect to the weight of the dried PPS) is preferably 0.5 or more, more preferably 3 or more, and even more preferably 5 or more.

In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having excellent retention stability, residual oligomers and residual salts were removed by repeating organic solvent washing and washing with warm water at about 80 ° C. or the above-mentioned hot water washing several times. After that, a method of treating with an acid or an alkali metal salt or an alkaline earth metal salt is preferable, and a method of treating with an alkali metal salt or an alkaline earth metal salt is more preferable.

In addition, (a) the PPS resin can be used after the polymerization is completed by heating in an oxygen atmosphere and by performing thermal oxidative cross-linking treatment by adding a cross-linking agent such as a peroxide to increase the molecular weight.

In the case of dry heat treatment for the purpose of increasing the molecular weight by thermal oxidative crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. Further, it is desirable that the oxygen concentration is 5% by volume or more, more preferably 8% by volume or more. The upper limit of the oxygen concentration is not particularly limited, but is limited to about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, still more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer, a rotary type or a heating device with a stirring blade, but for efficient and more uniform treatment, heating with a rotary type or a stirring blade. It is more preferable to use the device.

It is also possible to perform dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatile components. The temperature is preferably 130 to 250 ° C, more preferably 160 to 250 ° C. Further, the oxygen concentration in this case is preferably less than 5% by volume, more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, still more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer, a rotary type or a heating device with a stirring blade, but for efficient and more uniform treatment, heating with a rotary type or a stirring blade. It is more preferable to use the device.

However, from the viewpoint of exhibiting excellent toughness, the (a) PPS resin of the present invention is a substantially linear PPS resin that is not polymerized by thermal oxidative cross-linking treatment, or is lightly oxidatively cross-linked. It is preferably a semi-crosslinked PPS resin. Further, in the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

From the viewpoint of improving compatibility with (b) molten fluororesin and (c) olefin resin, the (a) PPS resin of the present invention preferably has a reactive functional group, and is specifically mentioned. Preferably contains at least one functional group selected from an amino group, an epoxy group, a carboxyl group, a hydroxyl group, and an acid anhydride group. The content of the functional group is preferably 5 to 400 μmol / g, more preferably 10 to 250 μmol / g, further preferably 15 to 150 μmol / g, still more preferably 20 to 80 μmol / g. When the amount of the reactive functional group of the PPS resin is 5 μmol / g or more, the interaction with (b) the molten fluororesin and (c) the olefin resin tends to be improved, which is preferable. On the other hand, when the amount of reactive functional groups of the PPS resin is 400 μmol / g or less, the amount of volatile components in the processing step can be suppressed, which is preferable.

(A) As a method for introducing a reactive functional group into the PPS resin, a method for copolymerizing a polyhalogenated aromatic compound containing a functional group, a compound containing a functional group, or malean anhydride in the case of a carboxyl group. Examples thereof include a method of adding an acid, a sorbic acid, or the like and (a) introducing the PPS resin by reacting it while melt-kneading it.

(2) (b) Molten Fluororesin The molten fluororesin used in the present invention refers to a fluororesin to which a molding means that undergoes heat melting such as an extrusion molding method or an injection molding method performed on a general thermoplastic resin can be applied. ..

The structure of the molten fluororesin used in the present invention is not particularly limited, but it is essential that it is composed of at least one type of fluoroolefin. For example, homopolymers such as chlorotrifluoroethylene, copolymers with tetrafluoroethylene, hexafluoropropylene, perfluoro (alkyl vinyl ether), vinylidene fluoride, vinyl fluoride, and ethylene, propylene, butene, alkyl. A copolymer with a non-fluoroethylene monomer containing no fluorine such as vinyl ethers can also be exemplified. More specifically, ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene. Examples thereof include -tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), and polychlorotrifluoroethylene (PCTFE). Among them, ETFE, PFA, and FEP are used from the viewpoint of easy melt molding. , PVDF is preferred, and ETFE, PFA, FEP are particularly preferred. Polytetrafluoroethylene (PTFE) is not preferable because it is difficult to perform melt processing represented by injection molding.

It is also preferable that the molten fluororesin used in the present invention contains a reactive functional group from the viewpoint of forming an intermolecular bond with the PPS resin or the olefin resin.

The reactive functional group is not particularly limited, and specifically, a vinyl group, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, an aldehyde group, a carbonyldioxy group, a haloformyl group, an alkoxycarbonyl group and an amino group. Examples include groups, hydroxyl groups, styryl groups, methacrylic groups, acrylic groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, hydrolyzable silyl groups, etc. Among them, hydroxyl groups, epoxy groups, carboxyl groups, amino groups and acid anhydrides. A physical group and an isocyanate group are preferable, and two or more of these reactive functional groups may be contained.

As a method of introducing a reactive functional group into the molten fluorine resin, a method of blending a compound or a resin that is compatible with the molten fluorine resin and containing the functional group, or a method of polymerizing the molten fluorine resin, the functional group A method of copolymerizing a polymerizable monomer containing a functional group capable of converting into the functional group into a main chain, a side chain or a terminal, and whether the functional group is contained when the molten fluororesin is polymerized. A method using an initiator containing a functional group that can be converted into a functional group, a method using a molten fluororesin and a polymerizable monomer that contains the functional group or contains a functional group that can be converted into the functional group, and the presence of a radical generator. Examples thereof include a method of reacting below and a method of modifying a molten fluororesin by a method such as oxidation or thermal decomposition. Among them, a method of copolymerizing a polymerizable monomer containing the functional group or a functional group capable of converting into the functional group into the main chain, side chain or terminal when polymerizing the molten fluorine resin, the molten fluorine resin. A method of reacting the above functional group with a polymerizable monomer containing the functional group or a functional group capable of converting into the functional group in the presence of a radical generator is preferable from the viewpoint of quality, cost and control of introduction amount.

The polymerizable monomer containing the functional group is not particularly limited, but for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, their acid anhydrides, and acrylic acid. Examples thereof include glycidyl, glycidyl methacrylate, glycidyl ethylacrylate, glycidyl itaconic acid, vinyl acetate, vinyl propionate, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

The amount of the functional group contained in the molten fluororesin is preferably 0.01 mol% or more with respect to 1 mol of (b) the molten fluororesin from the viewpoint of (a) the reaction with the PPS resin sufficiently proceeds. It is more preferably 0.05 mol% or more, and further preferably 0.1 mol% or more. The upper limit of the amount of functional groups is not particularly limited as long as the original characteristics of the molten fluororesin are not impaired, and is preferably 10 mol% or less, more preferably 3 mol% or less in consideration of deterioration of fluidity and the like. It can be exemplified as a range.

The blending amount of (b) molten fluororesin in the embodiment of the present invention is 32% by volume or more and 99% by volume in a total of 100% by volume of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin. The following are indispensable, preferably 32% by volume or more and 90% by volume or less, and more preferably 34% by volume or more and 80% by volume or less. If the molten fluororesin exceeds 99% by volume, the strength of the resin composition decreases, which is not preferable from the viewpoint of maintaining the shape of the molded product. Further, if the molten fluororesin is less than 32% by volume, it tends to be difficult to achieve both desired tracking resistance and toughness. Further, the combined use of two or more kinds of molten fluororesins is also effective in imparting tracking resistance and toughness characteristics.

The melting point of the molten fluororesin used in the embodiment of the present invention is preferably 340 ° C. or lower, more preferably 300 ° C. or lower, still more preferably 280 ° C. or lower. The lower limit of the melting point is preferably 150 ° C. or higher, more preferably 190 ° C. or higher, from the viewpoint of heat resistance of the fluororesin at the PPS resin processing temperature. On the other hand, in the case of a fluororesin having a melting point of more than 340 ° C., the temperature at which melt-kneading is performed becomes higher, so that the PPS resin deteriorates, leading to deterioration of mechanical properties and the like.

The MFR of the molten fluororesin used in the embodiment of the present invention is preferably 0.1 to 300 g / 10 minutes, and more preferably 0.1 to 100 g / 10 minutes. The above MFR range is desirable for forming a desired phase-separated structure, and if it is below the range, the extrusion processability is inferior, and if it exceeds the range, the mechanical properties are inferior.

As an example of the above-mentioned MFR measurement method, in the case of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a nozzle having a diameter of 2 mm and a length of 10 mm is used for 10 minutes at 372 ° C. and a 5 kg load specified in ASTM-D3307 (2010). It is defined by the amount of passage (g / 10 minutes). Further, in the case of the tetrafluoroethylene-hexafluoropropylene copolymer, the same passing amount as specified in ASTM-D2116 (2007) at 372 ° C. and a load of 5 kg is used, and in the case of the ethylene-tetrafluoroethylene copolymer, ASTM -D3159 (2010), respectively, defined as similar passages at 297 ° C. and 5 kg load.

(3) (c) Olefin Resin It is essential to add an olefin resin to the PPS resin composition according to the embodiment of the present invention in order to achieve both excellent tracking resistance and high toughness of the resin composition.

Specific examples of such olefin resins include homopolymers such as ethylene, propylene and methylpentene, and α-olefins and cycloolefins such as ethylene, propylene, methylpentene, 1-butene, 1-hexene and 1-octene. Copolymers using two or more kinds from the above, one or more kinds of α-olefins such as ethylene, propylene, methylpentene, 1-butene, 1-hexene, 1-octene and vinyl acetate, ethyl acrylate, acrylic acid Examples thereof include copolymers with methyl, glycidyl methacrylate, butyl acrylate, methyl acrylate, styrene and the like. More specifically, polyethylene, polypropylene, polymethylpentene, ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, Ethylene-methyl acrylate copolymer, ethyl ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-styrene copolymer, Examples thereof include an ethylene-methyl acrylate-glycidyl methacrylate copolymer, an ethyl ethylene-ethyl acrylate-glycidyl methacrylate copolymer, and an ethylene-vinyl acetate-glycidyl methacrylate copolymer.

Among them, ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic Ethyl acid acid copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-styrene copolymer, ethylene-methyl glycidyl methacrylate copolymer , Ethyl-acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer and other olefin-based elastomers are preferable.

It is also preferable that the olefin resin used in the present invention contains a reactive functional group from the viewpoint of forming an intermolecular bond with the PPS resin or the molten fluororesin.

The reactive functional group of the olefin resin is not particularly limited, and specifically, a vinyl group, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, an aldehyde group, a carbonyldioxy group, a haloformyl group, and an alkoxy. Examples thereof include carbonyl group, amino group, hydroxyl group, styryl group, methacryl group, acrylic group, ureido group, mercapto group, sulfide group, isocyanate group and hydrolyzable silyl group. Among them, hydroxyl group, epoxy group, carboxyl group and amino. A group, an acid anhydride group, and an isocyanate group are preferable, and two or more of these reactive functional groups may be contained.

As a method of introducing a reactive functional group into an olefin resin, a method of blending a compound or a resin that is compatible with the olefin resin and containing the functional group, or a method of blending the functional group when polymerizing the olefin resin is performed. A method of copolymerizing a polymerizable monomer containing a functional group convertible into the functional group into a main chain, a side chain or a terminal, or when polymerizing an olefin resin, the functional group is contained or converted into the functional group. A method using an initiator containing a possible functional group, a method of reacting an olefin resin with a polymerizable monomer containing the functional group or containing a functional group convertible into the functional group in the presence of a radical generator. , A method of modifying an olefin resin by a method such as oxidation or thermal decomposition. Among them, when polymerizing an olefin resin, a method of copolymerizing a polymerizable monomer containing the functional group or a functional group capable of converting into the functional group into a main chain, a side chain or a terminal, the olefin resin and the above. A method of reacting a polymerizable monomer containing a functional group or a functional group capable of converting into the functional group in the presence of a radical generator is preferable from the viewpoint of quality, cost, and control of introduction amount.

The polymerizable monomer containing the functional group is not particularly limited, but for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, their acid anhydrides, and acrylic acid. Examples thereof include glycidyl, glycidyl methacrylate, glycidyl ethylacrylate, glycidyl itaconic acid, vinyl acetate, vinyl propionate, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

The amount of functional groups contained in the olefin resin is 0.01 weight with respect to the weight of (c) olefin resin from the viewpoint that the reaction with (a) PPS resin and (b) molten fluororesin proceeds sufficiently. % Or more is preferable, 0.1% by weight or more is preferable, and 1% by weight or more is more preferable. The upper limit of the amount of functional groups is not particularly limited as long as the original characteristics of the olefin resin are not impaired, and in consideration of deterioration of fluidity, 40% by weight or less is preferable, and 30% by weight or less is more preferable. Can be exemplified as.

The blending amount of the olefin resin in the embodiment of the present invention is 100% by volume in total of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin, and 1% by volume in total of PPS resin and olefin resin. It is indispensable that it is 68% by volume or more, preferably 10% by volume or more and 68% by volume or less, and further preferably 20% by volume or more and 66% by volume or less. When the total of the PPS resin and the olefin resin exceeds 68% by volume, it tends to be difficult for the tracking resistance of the resin composition to achieve rank 0. On the other hand, when the total of the PPS resin and the olefin resin is less than 1% by volume, the strength of the resin composition decreases, which is not preferable from the viewpoint of maintaining the shape of the molded product.

The ratio of the PPS resin to the olefin resin is 5% by volume or more and 95% by volume or less of the olefin resin from the viewpoint of achieving both tracking resistance and toughness when the total of the PPS resin and the olefin resin is 100% by volume. Is preferable, and 10% by volume or more and 90% by volume or less is more preferable. It is also possible to use two or more types of olefin resins in combination.

(4) (d) Other additives Further, the PPS resin composition of the present invention is other than (a) PPS resin, (b) molten fluororesin and (c) olefin resin as long as the effects of the present invention are not impaired. Resin may be added and blended. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, and polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, and polyamideimide resins.

In addition, the following compounds can be added for the purpose of modification. Plastic agents such as polyalkylene oxide oligoma compounds, thioether compounds, ester compounds and organic phosphorus compounds, crystal nucleating agents such as organic phosphorus compounds and polyether ether ketones, waxes montanate, lithium stearate, aluminum stearate. Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, anticoloring agents such as hypophosphates, water, lubricants, ultraviolet inhibitors, coloring agents, foaming Ordinary additives such as agents can be blended. All of the above compounds are not preferable if they exceed 10 parts by weight based on 100 parts by weight of the total of the PPS resin, the molten fluororesin and the olefin resin, because the original characteristics of the resin composition of the present invention are impaired. More preferably, 1 part by weight or less is added.

Further, in the present invention, a compatibilizer can be used in combination for the purpose of enhancing compatibility between the resins. Specifically, epoxy resins and organic silane compounds can be exemplified.

Specific examples of such epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, special skeleton bifunctional epoxy resin having biphenyl skeleton, naphthalene skeleton and the like, cresol novolac type and trisphenol methane type. Glycidyl ether type epoxy resin typified by polyfunctional epoxy resin such as dicyclopentadiene type, glycidylamine type epoxy resin typified by aromatic amine type and aminophenol type, typified by hydrophthalic acid type and dimer acid type Glycidyl ester type epoxy resin can be mentioned.

The amount of the epoxy resin added is preferably 0.1 to 5 parts by weight, particularly 0.2 parts by weight, based on 100 parts by weight of the total of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin. ~ 3 parts by weight is preferable.

Specific examples of such organic silane compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysisilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Mercapto group-containing alkoxysilane compounds such as alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysisilane, γ- (2-) Ureidoethyl) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, Isocyanate group-containing alkoxysilane compounds such as γ-isocyanatepropylethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane, γ-isocyanatepropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2) -Aminoethyl) Aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- Examples thereof include organic silane compounds such as amino group-containing alkoxysilane compounds such as 3-aminopropyltrimethoxysilane, and among them, isocyanate group-containing alkoxysilane compounds are particularly preferable from the viewpoint of reactivity. On the other hand, an amino group-containing alkoxysilane compound is particularly preferable from the viewpoint of weld characteristics (tensile strength, tensile strain).

The amount of the organic silane compound added is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin, and particularly 0. 2 to 3 parts by weight is preferable.

Although it is not an essential component, the PPS resin composition of the present invention may be blended with an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of such inorganic fillers include glass fibers, carbon fibers, carbon nanotubes, carbon nanohorns, potassium titanate whiskers, zinc oxide whiskers, calcium carbonate whiskers, wallastenite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, and silicon carbide fibers. , Ceramic fiber, asbestos fiber, stone shaving fiber, metal fiber and other fibrous fillers, or fullerene, talc, wallastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silates such as silicate, silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, metal compounds such as iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and water. Hydrooxides such as calcium oxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, non-fibrous fillers such as graphite are used. Of these, glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of food-proofing materials and fillers. Further, these inorganic fillers may be hollow, and two or more kinds thereof can be used in combination. Further, these inorganic fillers may be pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound before use. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the effects of preventing foodstuffs, lubricants, and imparting conductivity.

The blending amount of the inorganic filler is selected in the range of less than 30 parts by weight with respect to 100 parts by weight of the total of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin, and is less than 20 parts by weight. The range is preferable, the range of less than 10 parts by weight is more preferable, and the range of 5 parts by weight or less is further preferable. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. The blending of the inorganic filler is effective for improving the strength of the material, but the blending of more than 30 parts by weight causes a decrease in toughness, which is not preferable.

(5) Method for Producing Resin Composition As a method for producing the PPS resin composition of the present invention, production in a molten state, production in a solution state, or the like can be used, but from the viewpoint of simplicity, the PPS resin composition in a molten state can be used. Manufacture is preferably used. For production in the molten state, melt-kneading with an extruder, melt-kneading with a kneader, or the like can be used, but from the viewpoint of productivity, melt-kneading with an extruder capable of continuously producing is preferably used. For melt-kneading with an extruder, one or more extruders such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, and an extruder such as a twin-screw single-screw extruder can be used. From the viewpoint of improving properties, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a quadruped extruder can be preferably used, and melt-kneading by a twin-screw extruder is most preferable.

A more specific method for melt-kneading is not necessarily limited to this, but the L / D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more, and kneading. It is preferable to use a twin-screw extruder having two or more parts, preferably three or more parts. The upper limit of L / D is not particularly limited, but 60 or less is preferable from the viewpoint of economy. Further, the upper limit of the kneading portion is not particularly limited, but it is preferably 10 or less from the viewpoint of productivity. The ratio of the kneading portion to the total length of the screw is preferably 15% or more, more preferably 20% or more, still more preferably 30% or more. When the ratio of the kneading portion to the total length of the screw is less than 15%, the kneading power is inferior, so that (c) the number average dispersion diameter of the olefin resin becomes coarse, and it is difficult to develop desired physical properties. On the other hand, the upper limit of the ratio of the kneading portion to the total length of the screw is preferably 70% or less from the viewpoint of preventing deterioration of the resin due to the generation of excessive shear heat generation during kneading.

As for the screw rotation speed, a method of kneading under the conditions of 150 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute is preferable.

The preferred cylinder temperature (° C.) range is preferably the highest melting point of the melting points of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin + 5 to 100 ° C., and is specific. The temperature is in the range of 280 to 400 ° C, more preferably 280 to 360 ° C, and even more preferably 280 to 330 ° C.

The mixing order of the raw materials at the time of melt-kneading is not particularly limited, but all the raw materials are blended and then melt-kneaded by the above method, and some raw materials are blended and then melt-kneaded by the above method. Either this and the remaining raw materials are mixed and melt-kneaded, or some of the raw materials are mixed and then the remaining raw materials are mixed using a side feeder during melt-kneading with a twin-screw extruder. May be used.

By kneading two of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin in advance, the dispersion component can be made finer and the deterioration of mechanical properties can be suppressed. In particular, a method in which (a) PPS resin and (c) olefin resin are mixed in advance to prepare a premixed product, and the remaining (b) molten fluororesin is individually supplied to an extruder and mixed has tensile breaking strain. It is preferable because it improves. The method of premixing is not particularly limited, and examples thereof include a method of (a) PPS resin and (c) olefin resin being blended and then melt-kneaded. The method of mixing the premixed product and (b) the molten fluororesin is not particularly limited, but the method of blending the premixed product and (b) the molten fluororesin and then melt-kneading the premixed product, Examples thereof include (b) a method of mixing the molten fluororesin using a side feeder after melt-kneading.

As for the small amount additive component, it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.

(6) PPS Resin Composition The PPS resin composition of the embodiment of the present invention has both excellent tracking resistance and high toughness typified by tensile breaking strain. In order to exhibit such characteristics, it is necessary to obtain a resin composition having (a) PPS resin, (b) molten fluororesin, and (c) olefin resin in a specific volume ratio.

For the first time, it has been found that the resin composition having a specific composition of the present invention can achieve both tracking resistance CTI rank 0 and high toughness.

In order to obtain a molded product used for evaluating the electrical characteristics and mechanical properties of the PPS resin composition of the present invention, it is preferable to obtain the composition by heating and melting it by an injection molding method or an extrusion molding method. The heating temperature at that time is preferably the highest melting point + 5 to 100 ° C. among the melting points of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin, and specifically, The range is 280 to 400 ° C., more preferably 280 to 360 ° C., and even more preferably 280 to 330 ° C.

The PPS resin composition of the embodiment of the present invention needs to have a tracking resistance (measured according to IEC60112), which is one of the electrical properties, of rank 0. Insulating members and gaskets of primary batteries and secondary batteries are required not to cause tracking failure from a low voltage (for example, 150V) to a maximum voltage of 600V.

The PPS resin composition of the embodiment of the present invention has a tensile breaking strain (dumbbell test piece (ISO527-2-1A), tensile speed 5 mm / min, 23 ° C., ISO527-), which is one of the physical property values indicating the toughness of the material. (Measured according to 1 and 2), 5% or more is preferable, 8% or more is more preferable, 12.5% or more is further preferable, and 20% or more is particularly preferable. From the viewpoint of suppressing fracture during actual use of insulating members and gaskets of primary batteries and secondary batteries, it is desirable that the tensile strain at break of the resin composition is 5% or more. The tensile fracture strain is preferably higher from the viewpoint of suppressing member fracture during actual use, and although there is no particular upper limit, it can be exemplified that it is substantially 500% or less. Further, the tensile strength is preferably 10 MPa or more, more preferably 15 MPa or more, still more preferably 20 MPa or more. If it is less than 10 MPa, it is not preferable from the viewpoint of maintaining the shape of the molded product and compressing / tensile creep deformation during long-term use. On the other hand, from the viewpoint of assembling property in actual use, the tensile strength is preferably 300 MPa or less, more preferably 200 MPa or less, further preferably 100 MPa or less, still more preferably 80 MPa or less.

The PPS resin composition of the embodiment of the present invention has a weld tensile breaking strain (counterflow weld dumbbell test piece (width 6 mm, width 6 mm,), which is one of the physical property values indicating the characteristics in the weld portion of the molded product made of the resin composition. Thickness 1.6 mm, distance between marked lines 50 mm, gates at both ends to form a weld joint surface in the center between marked lines), tensile speed 10 mm / min, distance between marked lines 50 mm, distance between chucks 64 mm, 23 ° C. 2% or more is preferable, 3% or more is more preferable, 4% or more is further preferable, and 5% or more is particularly preferable. From the viewpoint of suppressing breakage from the weld portion of the molded product during actual use in the insulating member or gasket of the primary battery or secondary battery, it is desirable that the weld tensile breaking strain of the resin composition is 2% or more. The weld tensile breaking strain is preferably higher from the viewpoint of suppressing member breaking during actual use, and although there is no particular upper limit, it can be exemplified that it is substantially 500% or less. The weld tensile strength is preferably 10 MPa or more, more preferably 15 MPa or more, and even more preferably 20 MPa or more. If it is less than 10 MPa, it is not preferable from the viewpoint of occurrence of breakage when assembling the molded product. From the viewpoint of suppressing member breakage during actual use, a higher value is preferable, and an upper limit is not particularly set, but it can be exemplified that it is substantially 100 MPa or less.

The PPS resin composition of the embodiment of the present invention has excellent chemical resistance. In addition to polar / non-polar organic solvents and acidic / alkaline aqueous solutions, it has excellent resistance to battery electrolytes, and the weight change before and after immersion in these solvents should be 1% or less. Preferably, 0.1% or less is more preferable, and 0.01% or less is more preferable. Examples of the electrolytic solution include, in the case of a lithium ion secondary battery, each simple substance or mixture of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, and an additive of lithium hexafluorophosphate. As a chemical resistance test method, a method of immersing a square plate (80 mm × 80 mm × 3.0 mm thickness) in 100 g of dimethyl carbonate and measuring the weight change before and after the treatment at 23 ° C. for 24 hours can be exemplified.

As the phase structure of the PPS resin composition of the embodiment of the present invention, both components (a) PPS resin and (b) molten fluororesin are present on the surface of the molded product made of the present composition, and (b) melt. It is preferable that the fluororesin forms a continuous phase.

By the presence of (a) PPS resin and (b) molten fluororesin on the surface of the molded product and (b) the molten fluororesin forming a continuous phase, the PPS resin originally has excellent heat resistance and chemical resistance. It leads to the development of excellent tracking resistance as well as low water absorption.

The method for obtaining such a phase structure on the surface of the molded product is not particularly limited, but for example, the total of (a) PPS resin, (b) molten fluororesin, and (c) olefin resin is 100% by volume. , (A) component and (c) component are preferably 1% by volume or more and 68% by volume or less, and (b) component is preferably 32% by volume or more and 99% by volume or less. Further, as a method for obtaining this phase structure, (b) the molten fluororesin and (c) the olefin resin are at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid anhydride group, and an isocyanate group. It is preferable to have.

The phase structure on the surface of the molded product is an ISO5272-1A dumbbell at a molding temperature of + 5 to 40 ° C., which is the higher melting peak temperature of (a) PPS resin and (b) molten fluororesin. A test piece can be molded and the central surface thereof can be evaluated by using a scanning electron microscope.

(7) Applications The polyphenylene sulfide resin composition of the present invention can be molded by various molding methods such as injection molding, extrusion molding, compression molding, injection molding, injection compression molding, etc., and is particularly useful for injection molding and extrusion molding. Is.

Further, since the polyphenylene sulfide resin composition of the present invention has tracking resistance and toughness in addition to the chemical resistance and heat resistance inherent in the PPS resin, it has electrical and electronic parts, communication equipment parts, automobile parts, and home appliance parts. , OA equipment parts and the like are suitable for use. In particular, since it retains electrical insulation in a wide temperature range up to high temperatures, it is also suitable for use as an electrical insulating member, and is particularly suitable for insulating members and gaskets of primary batteries and secondary batteries. As an insulating member or gasket for a primary battery or a secondary battery, it is arranged between each electrode current collector of the positive and negative electrodes and an electrode terminal, and is used for suppressing leakage of an electrolytic solution and for electrical insulation.

Primary or secondary batteries include alkaline manganese dry batteries, galvanized batteries, nickel-based primary batteries, lithium batteries, manganese dry batteries, mercury batteries, all-solid-state batteries and other primary batteries, lead storage batteries, lithium / air batteries, and lithium ion secondary batteries. , Lithium-ion polymer secondary battery, iron-iron phosphate lithium-ion battery, lithium / sulfur battery, nickel / cadmium storage battery, nickel / hydrogen rechargeable battery, nickel / lithium battery, nickel / zinc battery, all-solid-state battery, etc. Can be mentioned.

Other uses include round bars, square bars, sheets, films, tubes, pipes, etc. as molded products obtained by extrusion molding, and more specific uses include water heater motors, air conditioner motors, and drive motors. Electrical insulation materials for, film capacitors, speaker diaphragms, magnetic tapes for recording, printed board materials, printed board peripheral parts, semiconductor packages, semiconductor transport trays, process / release films, protective films, automotive film sensors, etc. Insulation tape for wire cables, insulation washers in lithium-ion batteries, hot water and cooling water, tubes for chemicals, fuel tubes for automobiles, hot water pipes, chemical pipes for chemical plants, ultra-pure water and ultra-high purity Examples thereof include piping for solvents, automobile piping, piping pipes for Freon and supercritical carbon dioxide refrigerants, and workpiece holding rings for polishing devices. In addition, wire harnesses and control wires for hybrid automobiles, electric automobiles, railways, coating moldings of windings for motor coils of power generation equipment, heat-resistant electric wire cables for home appliances, flat cables used for wiring in automobiles, communication, etc. Examples thereof include a coating molded body of windings of a signal transformer for transmission, high frequency, audio, measurement, etc. or an in-vehicle transformer, a spiral tube, and the like.

Applications of molded products obtained by injection molding include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, machine breakers, knife switches, and other poles. Electrical equipment parts such as rods and electric parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, condensers, variable condenser cases, optical pickups, oscillators, various terminal boards, metaphors, plugs , Printed boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electronic components; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademarks) / compact discs, lighting parts, refrigerator parts, typewriter parts, word processors Household and office electrical product parts represented by parts; Air conditioner parts represented by expansion valves, closing valves, check valves, service ports, refrigerant control valves, etc .; Office computer-related parts, telephone equipment-related parts, facsimile-related parts , Copier-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: Microscopes, binoculars, cameras, watches, and other optical equipment and precision machine-related parts; Alternator terminals, Alternator connector, IC regulator, potential meter base for light deer, various valves such as exhaust gas valve, various pipes and ducts related to fuel, exhaust system, intake system, turbo duct, air intake nozzle snorkel, intake manifold, fuel pump, engine Cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner , Heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust relay, starter switch , Starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, Automobile / vehicle-related parts such as brake pistons, solenoid bobbins, engine oil filters, ignition device cases, millimeter-wave radars; for primary or secondary batteries such as mobile phones, laptop computers, video cameras, hybrid vehicles, electric vehicles, etc. Insulation members and gaskets; gears, washers, screws, nuts, binding bands, pipe joints, nozzles, bearings, cages, seal rings, etc. can be exemplified.

Examples of the molded product obtained by other molding include lining, coating, bottle, tank and the like.

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

In Examples and Comparative Examples, the following were used as (a) PPS resin, (b) molten fluororesin (c) olefin resin.

[(A) PPS resin (a-1)]
a-1: Linear PPS resin Weight average molecular weight: 70000, carboxyl group weight: 33 μmol / g, melting point: 280 ° C., specific gravity: 1.35 g / cm ³
[(B) Molten fluororesin (b-1 to 4)]
b-1: Ethylene-tetrafluoroethylene copolymer containing an acid anhydride group (ETFE, AH-2000 manufactured by AGC Inc., melting point: 240 ° C., MFR: 22 g / 10 minutes (297 ° C., 5 kg load)), Reactive functional group amount: 0.4 mol%, specific gravity: 1.78 g / cm ³
b-2: Carboxylic acid group-containing ethylene-tetrafluoroethylene copolymer (ETFE, RP-5000 manufactured by Daikin Corporation, melting point: 195 ° C., MFR: 25 g / 10 minutes (265 ° C., 5 kg load)), reaction Amount of sex functional groups: 0.4 mol%, specific gravity: 1.75 g / cm ³
b-3: Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA, P-62XP manufactured by AGC Inc., melting point: 297 ° C., MFR: 24 g / 10 minutes (372 ° C., 5 kg load)), No reactive functional group, specific gravity: 2.15 g / cm ³
b-4: Ethylene-tetrafluoroethylene copolymer (ETFE, EP610 manufactured by Daikin Corporation, melting point: 225 ° C., MFR: 30 g / 10 minutes (297 ° C., 5 kg load)), no reactive functional group, specific gravity 1.86 g / cm ³
[(C) Olefin resin (c-1)]
c-1: Ethylene-glycidyl methacrylate copolymer (olefin resin manufactured by Sumitomo Chemical Co., Ltd., Bond First E, melting point 103 ° C., MFR: 3 g / 10 minutes (190 ° C., 21.2 N load)), reactive sensory Base weight: 12% by weight, specific gravity: 0.94 g / cm ³
[(D) Other additives (d-1 to 4)]
d-1: γ-Isocyanatepropyltriethoxysilane (KBE-9007N manufactured by Shin-Etsu Chemical Co., Ltd.)
d-2: Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd. Kisuma (registered trademark) 5E)
d-3: Glass fiber (T717H manufactured by Nippon Electric Glass Co., Ltd., average fiber diameter: 11 μm)
d-4: Polytetrafluoroethylene (PTFE: non-molten fluororesin, PTFE manufactured by Daikin Corporation, Lubron L-5).
d-5: γ-Aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.)

In the following examples, the material properties were evaluated by the following method.

[Tensile test]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., an ISO5272-1A dumbbell test piece was molded at a resin temperature of 310 ° C. and a mold temperature of 150 ° C. With respect to the obtained test piece, the tensile strength and the tensile breaking strain were measured according to ISO527-1, 2 under the conditions of a distance between fulcrums of 114 mm, a tensile speed of 5 mm / min, a temperature of 23 ° C., and a relative humidity of 50%.

[Weld tensile test]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., at a resin temperature of 300 ° C. and a mold temperature of 150 ° C., gates are provided at both ends to form a countercurrent weld joint surface in the center between marked lines. A dumbbell test piece was molded. The shape of the test piece is dumbbell thickness: 1.6 mm, width: 6 mm, distance between marked lines: 50 mm. Weld tensile strength and weld tensile breaking strain were measured for the obtained test piece under the conditions of a distance between fulcrums of 64 mm, a tensile speed of 10 mm / min, a temperature of 23 ° C., and a relative humidity of 50%.

[Weight average molecular weight of PPS resin]
The weight average molecular weight (Mw) of the PPS resin was calculated in terms of polystyrene using gel permeation chromatography (GPC). The measurement conditions of GPC are shown below.
Device: SSC-7110 (Senshu Science)
Column name: Shodex UT806M x 2
Eluent: 1-chloronaphthalene detector: differential refractive index detector Column temperature: 210 ° C
Pre-constant temperature bath temperature: 250 ° C
Pump constant temperature bath temperature: 50 ° C
Detector temperature: 210 ° C
Flow rate: 1.0 mL / min
Sample injection amount: 300 μL (slurry: about 0.2% by weight).

[Amount of carboxyl groups in PPS resin]
The carboxyl group content of the PPS resin was calculated using a Fourier transform infrared spectroscope (hereinafter abbreviated as FT-IR).

First, benzoic acid was measured by FT-IR as a standard substance, and the absorption intensity (b1) of the peak of 3066 cm ^-1 , which is the absorption of the CH bond of the benzene ring, and the peak of 1704 cm ^-1 , which is the absorption of the carboxyl group. The absorption intensity (c1) of the above was read, and the amount of carboxyl groups (U1) and (U1) = (c1) / [(b1) / 5] with respect to one unit of the benzene ring were determined. Next, the PPS resin was melt-pressed at 320 ° C. for 1 minute and then rapidly cooled to perform FT-IR measurement of the obtained amorphous film. 3066cm reads absorption intensity of ^-1 (b2) and absorption intensity of 1704cm ^-1 (c2), a carboxyl group amount with respect to the benzene ring by one unit (U2), a (U2) = (c2) / [(b2) / 4] I asked. The carboxyl group content with respect to 1 g of PPS resin was calculated from the following formula. Amount of carboxyl groups in PPS resin (μmol / g) = (U2) / (U1) /108.161 × 1000000

[Tracking resistance]
Compliant with IEC60112 4th edition using a square plate (80 mm x 80 mm x 3.0 mm thickness) molded at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C with an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries. Then, the maximum voltage at which tracking failure does not occur was obtained. Measure the maximum voltage that can withstand the measurement time of 50 drops without destroying 5 test pieces, and then measure 100 drops of 5 test pieces at a voltage 25 V lower than the maximum voltage obtained by measuring 50 drops. It was measured whether it could withstand the measurement of. A 0.1% ammonium chloride aqueous solution was used as the electrolytic solution.

In Table 1, when tracking destruction did not occur in the measurement of 50 drops at 25V increments from 150 to 600V and no tracking destruction occurred in the measurement of 100 drops at 575V, it was judged as CTI rank 0, and ◯. It is indicated by a mark, and when tracking failure occurs in the measurement of 50 drops in 25 V increments from 150 to 600 V, it is indicated by a cross.

[Phase structure on the surface of the molded product]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., an ISO5272-1A dumbbell test piece was molded at a resin temperature of 310 ° C. and a mold temperature of 150 ° C. The surface of the central portion of the obtained test piece was evaluated using a field emission scanning electron microscope (SU8220: manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 5 kV and a measurement magnification of 2000 times.

In Table 1, when both components of (a) PPS resin and (b) molten fluororesin are present and (b) molten fluororesin forms a continuous phase, they are marked with a circle and have other phase structures. The case is indicated by a cross.

[Examples 1 to 10, Comparative Examples 1 to 5]
The volume% of the PPS resin, the molten fluororesin, and the olefin resin was set as shown in Table 1, and the organic silane compound was dry-blended by the weight part shown in Table 1 with respect to 100 parts by weight of the total of the PPS resin, the molten fluororesin, and the olefin resin. After that, using a TEX30α twin-screw extruder (30 mmφ, L / D = 45) manufactured by Japan Steel Works equipped with a vacuum vent, the screw arrangement was made at 3 kneading parts, and the ratio of the kneading part to the total length of the screw was 30%. , The cylinder temperature was set to 320 ° C. and melt-kneaded. This manufacturing method is referred to as method A. Then, it was pelletized by a strand cutter. The obtained pellets were dried at 130 ° C. for 8 hours and then subjected to injection molding, and the obtained molded product was subjected to a tensile test, a tracking resistance test, a phase structure observation, and a weld tensile test.

[Examples 11 and 12]
After dry blending 68% by weight of PPS resin, 32% by weight of olefin resin and 1.37 parts by weight of organic silane compound (by weight part with respect to 100 parts by weight of PPS resin and olefin resin in total), manufactured by Japan Steel Works equipped with a vacuum vent. Using a TEX30α twin-screw extruder (30 mmφ, L / D = 45), the screw arrangement is set to 3 kneading parts, the ratio of the kneading part to the total length of the screw is 30%, and the cylinder temperature is set to 320 ° C. for melting. Kneaded. Then, it was pelletized by a strand cutter. After dry-blending 55% by volume of the obtained premixed PPS resin and olefin resin and 45% by volume of molten fluororesin, a TEX30α twin-screw extruder (30 mmφ, L / D =) manufactured by Japan Steel Works equipped with a vacuum vent. 45) was used, the screw arrangement was set at three kneading portions, the ratio of the kneading portion to the total length of the screw was 30%, and the cylinder temperature was set to 320 ° C. for melt kneading. The two-step main manufacturing method is referred to as method B. The obtained pellets were dried at 130 ° C. for 8 hours and then subjected to injection molding, and the obtained molded product was subjected to a tensile test, a tracking resistance test, a phase structure observation, and a weld tensile test. Table 1 shows the amount of each component finally blended in the resin composition.

[Comparative Example 6]
Japan provided a vacuum vent after the PPS resin and the olefin resin were dry-blended by the weights shown in Table 1 with respect to 100 parts by weight of the total of the PPS resin and the olefin resin. Using a TEX30α twin-screw extruder (30 mmφ, L / D = 45) manufactured by Japan Steel Works, the screw arrangement is set to 3 kneading parts, the ratio of the kneading part to the total length of the screw is 30%, and the cylinder temperature is set to 320 ° C. And melt-kneaded. With respect to a total of 100 parts by weight of the PPS resin and the olefin resin, the weight parts of the glass fibers shown in Table 1 were charged using a side feeder. Then, it was pelletized by a strand cutter. The obtained pellets were dried at 130 ° C. for 8 hours and then subjected to injection molding, and the obtained molded products were subjected to a tensile test and a tracking resistance test.

[Comparative Example 7]
The PPS resin, the olefin resin, and PTFE were set to the volume% shown in Table 1, and the organic silane compound was dry-blended with respect to 100 parts by weight of the total of the PPS resin, the olefin resin, and PTFE in the parts by weight shown in Table 1, and then Examples. Under the same conditions as in No. 1, melt kneading, molding, and physical property evaluation were performed.

The results of the above-mentioned Examples and Comparative Examples will be described.

In Examples 1 to 12, by setting (a) PPS resin, (b) molten fluororesin, and (c) olefin resin to a specific volume composition, a tensile breaking strain of 5% or more is exhibited and excellent toughness is exhibited. Moreover, even in the tracking test, good results are shown in the range of 150 to 600 V. Examples 9 and 10 with γ-aminopropyltriethoxysilane exhibit excellent weld properties. Further, Examples 11 and 12 adopting the two-step kneading method show excellent tensile breaking strain.

On the other hand, in Comparative Example 1 in which the compositions of the components (a), (b) and (c) deviate from the specific volume composition of the present invention, although they show excellent toughness, tracking failure occurs in the voltage range of 200 to 300 V in the tracking test. Therefore, a resin composition having sufficient tracking resistance cannot be obtained.

Further, (c) Comparative Examples 2 to 4 in which the olefin resin was not used in combination showed excellent toughness, but in the tracking test, tracking fracture occurred in the voltage range of 200 to 300 V, and the resin had sufficient tracking resistance. No composition is available.

(B) Comparative Example 5 in which the molten fluororesin was not used in combination showed excellent toughness, but in the tracking test, a resin composition having tracking fracture occurred in the voltage range of 200 to 300 V and had sufficient tracking resistance. I can't get it.

In Comparative Example 6 using magnesium hydroxide, which is a known technique for improving tracking resistance, although good tracking resistance is exhibited, a large amount of inorganic filler is used in combination, so that tensile strain at break is significantly reduced and toughness is increased. Inferior.

Compared with Example 1, in Comparative Example 7 in which PTFE was used instead of the molten fluororesin, the resin composition which caused tracking failure in the voltage range of 200 to 300 V in the tracking test and had sufficient tracking resistance was obtained. I can't get it. In addition, the tensile breaking strain is also significantly reduced, resulting in poor toughness.

Claims (9)

A resin composition obtained by blending (a) a polyphenylene sulfide resin, (b) a molten fluororesin, and (c) an olefin resin, and the sum of the components (a), (b), and (c) A polyphenylene sulfide resin composition in which the total of the components (a) and (c) is 1% by volume or more and 68% by volume or less, and the component (b) is 32% by volume or more and 99% by volume or less, assuming 100% by volume. A polyphenylene sulfide resin composition having rank 0 tracking resistance in a tracking resistance test (IEC60112) of a test piece obtained by injection molding the resin composition. The polyphenylene sulfide resin composition according to claim 1, which has a tensile breaking strain of 5% or more in a tensile test (ISO527-1 and 2) of a test piece obtained by injection molding the resin composition. Resin composition. The polyphenylene sulfide resin composition according to any one of claims 1 to 2, wherein the component (c) is selected from a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid anhydride group, and an isocyanate group. A polyphenylene sulfide resin composition which is an olefin resin having at least one functional group. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the component (c) is an olefin elastomer. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the component (b) is selected from a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid anhydride group, and an isocyanate group. A polyphenylene sulfide resin composition which is a molten fluororesin having at least one functional group. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein the component (b) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer or a hexafluoropropylene-tetrafluoroethylene copolymer. A polyphenylene sulfide resin composition which is at least one molten fluororesin selected from a coalescence and an ethylene-tetrafluoroethylene copolymer. An insulating member for a primary or secondary battery comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 6. A gasket for a primary or secondary battery comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 6. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 to 6, wherein (a) the polyphenylene sulfide resin and (c) the olefin resin are mixed in advance to form a premixed product, and the rest. (B) A method for producing a polyphenylene sulfide resin composition, which comprises supplying the molten fluororesin individually to an extruder.