KR20220002719A - Resin composition for gasket, production method therefor, and gasket for secondary battery - Google Patents

Abstract

Provided are a gasket material used for a sealed secondary battery (storage battery) such as a lithium ion secondary battery, a resin composition for a gasket having an excellent cavity balance and high mechanical strength, a manufacturing method thereof, and a gasket for a secondary battery. Specifically, as a resin composition for a gasket used in a secondary battery composed of a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte, it contains a polyarylene sulfide resin and a silicone compound, and the polyarylene sulfide resin is It relates to a resin composition for a gasket, a method for producing the same, and a gasket for a secondary battery, which can be obtained by a method comprising reacting in a molten mixture containing iodo aromatic compound, single sulfur and the polymerization inhibitor.

Description

Resin composition for gasket, its manufacturing method, and gasket for secondary batteries TECHNICAL FIELD

The present invention relates to a resin composition for a gasket used for a gasket of a secondary battery, a manufacturing method thereof, and a gasket for a secondary battery.

A sealed secondary battery is a battery case (exterior) in which a battery element containing a positive electrode plate, a negative electrode plate, and a separator disposed between the positive electrode plate and the negative electrode plate, and a battery element containing an electrolyte for immersing the electrode plate group are partially opened. sieve), and is sealed by a sealing member for sealing the opening of the battery case. In addition, in this sealed secondary battery, for example, a contact between the positive electrode and the positive terminal electrically connected to the positive electrode plate, or the contact between the negative electrode and the negative terminal electrically connected to the negative electrode, for preventing a short circuit between a pair of terminals or electrolyte solution A gasket is provided to prevent leakage. This gasket is required to have electrolyte resistance to the electrolyte and excellent airtightness.

In order to satisfy these requirements, for example, the technique of using the polyamide resin which improved heat-and-moisture resistance as a gasket material is reported (refer patent document 1, for example). However, although heat-and-moisture resistance can be slightly improved by using the polyamide resin with improved heat-and-moisture resistance, the degree of electrolyte resistance and airtightness are still insufficient.

On the other hand, it has been reported that a gasket using polyarylene sulfide resin or tetrafluoroethylene-per-fluoroalkylvinyl ether copolymer resin as a gasket material has excellent airtightness and electrolyte resistance (for example, Patent Literature see 2).

Japanese Patent Laid-Open No. 2005-78890 Japanese Patent Laid-Open No. 8-321287

In recent years, by using an active material having a high theoretical capacity as an electrode material, a high capacity lithium ion battery has progressed, while a large volume change of 3 to 4 times during charging and discharging is exhibited, and the pressure of the internal medium is remarkably high. In addition, as the specific gravity of vehicle-mounted applications such as hybrid vehicles (HV) and electric vehicles (EV) has increased, higher safety is required, and the reliability of the gasket under harsh conditions of high temperature and high humidity is extremely high. The level is becoming necessary.

However, the conventional gasket material cannot withstand the pressure of the internal medium, and does not reach the level required for a sealed secondary battery (storage battery) such as a lithium ion secondary battery that has been recently demanded, and is insufficient as a material. Therefore, it is calculated|required by the gasket material to improve mechanical strength.

On the other hand, when a plurality of gaskets are simultaneously molded by injection molding using a mold having a plurality of cavities, a molding defect in that some cavities are not sufficiently filled with a molding material may occur. Therefore, it is also calculated|required that the material for shaping|molding can be filled uniformly and nonuniformly.

Therefore, the main problem to be solved by the present invention is a gasket material used in sealed secondary batteries (storage batteries) such as lithium ion secondary batteries, excellent in cavity balance and high mechanical strength, resin composition for gaskets, and its manufacture To provide a method and a gasket for a secondary battery.

As a result of various studies, the present inventors have prepared a polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, single sulfur, and a polymerization inhibitor, and a resin composition containing a silicone compound. By using, it discovered that the said subject could be solved, and came to complete this invention.

That is, the present invention is a resin composition for a gasket used in a secondary battery composed of a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte, and contains a polyarylene sulfide resin and a silicone compound, and the polyarylene sulfide resin is , a gasket obtainable by a method comprising reacting a diiodo aromatic compound, single sulfur, and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, single sulfur and a polymerization inhibitor. A resin composition for use is provided. The present invention also provides a gasket for a secondary battery comprising the resin composition for the gasket.

The present invention also provides a method for producing a resin composition for a gasket used in a secondary battery composed of a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte, comprising a step of mixing a polyarylene sulfide resin and a silicone compound; Arylene sulfide resin can be obtained by a method comprising reacting a diiodo aromatic compound, single sulfur, and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, single sulfur and a polymerization inhibitor. There is provided a method for producing a resin composition for a gasket.

According to the present invention, there is provided a resin composition for a gasket used for a sealed secondary battery (storage battery) such as a lithium ion secondary battery, which has excellent cavity balance and high mechanical strength, a manufacturing method thereof, and a gasket for a secondary battery can do. Moreover, by using the said resin composition for gaskets, the gasket for secondary batteries which suppressed the gas generation by heating can be produced.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the test piece used for a compressive stress relaxation test.

EMBODIMENT OF THE INVENTION Hereinafter, suitable embodiment of this invention is demonstrated in detail. However, this invention is not limited to the following embodiment.

The resin composition for gaskets according to the present embodiment contains polyarylene sulfide resin and a silicone compound.

The polyarylene sulfide resin used in the present embodiment is obtained by reacting a diiodo aromatic compound, single sulfur, and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, single sulfur compound and a polymerization inhibitor. It can be obtained by a method comprising According to this method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods including the Phillips method.

The diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to the aromatic ring. Examples of the diiodo aromatic compound include diiodobenzene, diiodotoluene, diiodoxylene, diiodonnaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododi Although phenylsulfone etc. are mentioned, It is not limited to these. Although the substitution position of two iodine atoms is not specifically limited, Preferably, it is preferable that the two substitution positions are as far as possible in a molecule|numerator. Preferred substitution positions are the para position, and the 4,4'-position.

The aromatic ring of the diiodo aromatic compound is at least one selected from a phenyl group, a halogen atom other than an iodine atom, a hydroxyl group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone, and an arylketone. It may be substituted by the substituent of a species. However, from the viewpoint of crystallinity and heat resistance of the polyarylene sulfide resin, the ratio of the substituted diiodo aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001 to 5 mass%, and more Preferably it is the range of 0.001-1 mass %.

Single sulfur means a substance (S ₈ , S ₆ , S ₄ , S _{2 ,} etc.) composed of only sulfur atoms, and the form is not limited. Specifically, the organization may use the sulfur in the market as a military (局方) drugs may be used a mixture containing a universally available, such as S ₈ and S _6. The purity of the simple substance sulfur is not particularly limited, either. As long as simple sulfur is solid at room temperature (23 degreeC), granular form or powder form may be sufficient as it. Although the particle size of single sulfur is not specifically limited, Preferably it is the range of 0.001-10 mm, More preferably, it is the range of 0.01-5 mm, More preferably, it is the range of 0.01-3 mm.

A polymerization inhibitor can be used without a restriction|limiting in particular, as long as it is a compound which inhibits or stops the said polymerization reaction in the polymerization reaction of polyarylene sulfide resin. The polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group and a salt of a carboxyl group at the terminal of the main chain of the polyarylene sulfide resin. That is, as a polymerization inhibitor, the compound which has 1 or 2 or more of at least 1 sort(s) of group selected from the group which consists of a hydroxy group, an amino group, a carboxy group, and a salt of a carboxy group is preferable. Moreover, the polymerization inhibitor may have the said functional group, and may produce|generate the said functional group by the stop reaction of superposition|polymerization, etc.

As the polymerization inhibitor having a hydroxyl group or an amino group, for example, a compound represented by the following formula (1) or (2) can be used as the polymerization inhibitor.

According to the compound represented by the general formula (1), a monovalent group represented by the following formula (1-1) is introduced as a terminal group of the main chain. Y in Formula (1-1) is a hydroxyl group, an amino group, etc. which originate in a polymerization inhibitor.

According to the compound represented by the general formula (2), a monovalent group represented by the following formula (2-1) is introduced as a terminal group of the main chain. A hydroxy group derived from the compound represented by the general formula (1) can be introduced into the polyarylene sulfide resin, for example, by bonding with a carbon atom of the carbonyl group in the formula (2) and a sulfur radical.

The group represented by the formula (1-1) or (2-1) is sulfur generated by radical cleavage of a disulfide bond derived from a raw material (single sulfur) in the main chain of the polyarylene sulfide resin under melting temperature. When a radical and the compound represented by General formula (1) or the compound represented by General formula (2) couple|bond together, it is thought that it introduce|transduces in polyarylene sulfide resin. Presence of the structural unit of these specific structures is characteristic of polyarylene sulfide resin obtained by melt polymerization using the compound represented by General formula (1) or (2).

As a compound represented by General formula (1), 2-iodophenol, 2-amino aniline, etc. are mentioned, for example. As a compound represented by General formula (2), 2-iodobenzophenone is mentioned.

As the polymerization inhibitor having a carboxyl group, for example, one or more compounds selected from compounds represented by the following general formulas (3), (4) or (5) can be used.

In the general formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following general formulas (a), (b) or (c), and among ^{R 1} or R ² At least one of them is a monovalent group represented by the general formula (a), (b) or (c). In the general formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent value represented by the following general formula (a), (b) or (c). In the general formula (5), R ⁴ represents a monovalent group represented by the general formula (a), (b) or (c).

Although X in general formulas (a)-(c) is a hydrogen atom or an alkali metal atom, a hydrogen atom is preferable at the point which reactivity becomes favorable. Examples of the alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, but sodium is preferable. In the general formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In the general formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms.

According to the compound represented by the general formula (3), (4) or (5), a monovalent group represented by the following formula (6) or (7) is introduced as a terminal group of the main chain. Presence of the structural unit at the terminal of these specific structures is characteristic of polyarylene sulfide resin obtained by melt polymerization using the compound represented by General formula (3), (4) or (5).

(In the formula, R ⁵ represents a monovalent group represented by the general formula (a), (b) or (c))

(wherein R ⁶ represents a monovalent group represented by the general formula (a), (b) or (c))

As a polymerization inhibitor, you may use the compound etc. which do not have functional groups, such as a carboxy group. Examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothia. At least one compound selected from zolylsulfenamide, 2-(morpholinothio)benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.

The polyarylene sulfide resin according to the present embodiment is produced by performing melt polymerization in a molten mixture obtained by heating a mixture containing a diiodo aromatic compound, single sulfur, a polymerization inhibitor, and, if necessary, a catalyst. do. The ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 moles, more preferably in the range of 0.8 to 1.2 moles, based on 1 mole of single sulfur. Moreover, to [ the ratio of the polymerization inhibitor in a mixture / 1 mol of solid sulfur ], Preferably it is the range of 0.0001-0.1 mol, More preferably, it is the range of 0.0005-0.05 mol.

The timing of adding the polymerization inhibitor is not particularly limited, but the mixture containing the diiodo aromatic compound, single sulfur and optionally added catalyst is heated so that the temperature of the mixture is preferably 200°C to 320°C. The polymerization inhibitor may be added at a time in the range, more preferably in the range of 250 to 320°C.

The rate of polymerization can be controlled by adding a nitro compound as a catalyst to the molten mixture. As this nitro compound, various nitrobenzene derivatives can be used normally. As the nitrobenzene derivative, for example, 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diio do-4-nitroamine. The quantity of a catalyst may just be the quantity normally added as a catalyst, For example, it is preferable that it is the range of 0.01-20 mass parts with respect to 100 mass parts of single-piece sulfur.

The conditions of melt polymerization are suitably adjusted so that a polymerization reaction may advance suitably. The temperature of melt polymerization is preferably in the range of 175°C or higher, the melting point of the polyarylene sulfide resin to be produced +100°C or less, and more preferably in the range of 180 to 350°C. The melt polymerization is preferably carried out in an absolute pressure range of 1 [cPa] to 100 [kPa], more preferably 13 [cPa] to 60 [kPa]. The conditions of melt polymerization do not need to be constant. For example, in the initial stage of polymerization, the temperature is preferably in the range of 175 to 270°C, more preferably in the range of 180 to 250°C, and the absolute pressure is in the range of 6.7 to 100 [kPa], and thereafter, Polymerization is carried out continuously or stepwise while raising and lowering the temperature, and in the latter stage of polymerization, the temperature is preferably in the range of 270° C. or higher, and the melting point of the polyarylene sulfide resin to be produced is in the range of +100° C. or less, more preferably 300 to 350 The polymerization can be carried out in the range of deg. C and the absolute pressure in the range of 1 [cPa] to 6 [kPa]. In this specification, melting|fusing point of resin means the value measured based on JISK7121 using a differential scanning calorimeter (DSC apparatus Pyris Diamond manufactured by Perkin Elmer).

Melt polymerization is preferably performed in a non-oxidizing atmosphere from the viewpoint of obtaining a high degree of polymerization while preventing an oxidative crosslinking reaction. In a non-oxidizing atmosphere, the oxygen concentration of the gas phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, and even more preferably the gas phase is substantially free of oxygen. . The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium and argon.

Melt polymerization can be performed using, for example, a melt-kneader equipped with a heating device, a pressure reducing device, and a stirring device. As a melt-kneader, a Banbury mixer, a kneader, a continuous kneader, a single screw extruder, and a twin screw extruder are mentioned, for example.

It is preferable that the molten mixture for melt polymerization contains substantially no solvent. More specifically, the amount of the solvent contained in the molten mixture is preferably 10 parts by mass relative to 100 parts by mass in total of the diiodo aromatic compound, single sulfur, a polymerization inhibitor, and, if necessary, the catalyst. The following range, More preferably, it is the range of 5 mass parts or less, More preferably, it is the range of 1 mass part or less. The amount of the solvent may be 0 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more.

After the molten mixture (reaction product) after melt polymerization is cooled to obtain a mixture in a solid state, the polymerization reaction may be further advanced by heating the mixture under reduced pressure or under atmospheric pressure in a non-oxidizing atmosphere. Thereby, not only can molecular weight be increased further, but since the produced|generated iodine molecule|numerator is sublimed and removed, the iodine atom density|concentration in polyarylene sulfide resin can be suppressed low. By cooling to a temperature preferably in the range of 100 to 260° C., more preferably in the range of 130 to 250° C., and still more preferably in the range of 150 to 230° C., a mixture in a solid state can be obtained. Heating after cooling to a solid state can be performed under the temperature and pressure conditions similar to melt polymerization.

Although the reaction product containing the polyarylene sulfide resin obtained by the melt polymerization process can be directly put into a melt-kneader as it is, the resin composition can be produced, but the solvent in which the reaction product dissolves in the reaction product. It is preferable to prepare a lysate by adding , and to take out the reaction product from the reaction apparatus in the state of the lysate, because not only the productivity is excellent but also the reactivity is further improved. The addition of the solvent in which the reaction product dissolves is preferably carried out after melt polymerization, but may be carried out later in the reaction of melt polymerization, and as described above, by cooling the molten mixture (reaction product) to obtain a solid mixture After that, the polymerization reaction may be further advanced by heating the mixture under pressure, under reduced pressure, or under atmospheric pressure in a non-oxidizing atmosphere. You may perform the process of preparing the said melt in a non-oxidizing atmosphere. In addition, the temperature of heat dissolution may be in the range above the melting point of the solvent in which the reaction product dissolves, preferably in the range of 200 to 350°C, more preferably in the range of 210 to 250°C, and it is preferable to carry out under pressure. .

The blending ratio of the solvent in which the reaction product dissolves, which is used to prepare the melt, is preferably in the range of 90 to 1000 parts by mass, more preferably in the range of 100 parts by mass of the reaction product containing polyarylene sulfide resin. It is preferably in the range of 200 to 400 parts by mass.

As a solvent in which the reaction product dissolves, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as the Phillips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidone Aliphatic cyclic amide compounds such as dinoic acid, ε-caprolactam, N-methyl-ε-caprolactam, hexamethyl phosphate triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide Amide compounds such as (DMA), etherified polyethylene glycol compounds such as polyethylene glycol dialkyl ether (which has a degree of polymerization of 2000 or less and an alkyl group having 1 to 20 carbon atoms), and tetramethylene sulfoxide, and dimethyl sulfoxide Sulfoxide compounds, such as seed (DMSO), are mentioned. Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4'-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxa Diazole, 2,5-diphenyloxazole, triphenylmethanol, N,N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, Pentachlorophenol, 1-benzyl-2-pyrrolidione, 9-fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrol Dinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o,o '-Biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thianthrene, 3-phenoxybenzyl alcohol, 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4, 4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenylphthalate, diphenylcarbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromodi Phenyl ether, pyrene, 9,9'-bi-fluorene, 4,4'-isopropylidene-diphenol, ε-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenylisophthalate, diphenyl and at least one solvent selected from the group consisting of terephthalate and 1-chloronaphthalene.

Since the reactivity becomes more favorable, it is preferable to melt-knead the said melt|dissolved material taken out from the reaction apparatus after performing a post-process and to prepare a resin composition with the said other component. Although it does not restrict|limit especially as a method of post-processing of a lysate, For example, the following method is mentioned.

(1) The lysate as it is or after adding an acid or base, the solvent is distilled off under reduced pressure or under normal pressure, and then the solid after solvent distillation is mixed with water and the solvent used for the lysate (or to a low molecular weight polymer). A method of washing once or twice or more with a solvent selected from the group consisting of organic solvents having an equivalent solubility in the case of an organic solvent), acetone, methyl ethyl ketone and alcohols, and further neutralizing, washing with water, filtration and drying.

(2) Solvents such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons in the lysate (soluble in the solvent of the lysate, and at least polyarylene sulfide A method of adding a poor solvent (a solvent that is a poor solvent) as a precipitating agent to the resin to precipitate a solid product containing a polyarylene sulfide resin and an inorganic salt, and filtering, separating, washing and drying the solid product.

(3) To the lysate, the solvent used in the lysate (or an organic solvent having an equivalent solubility to the low molecular weight polymer) is added and stirred, filtered to remove the low molecular weight polymer, and then water, acetone, methyl ethyl ketone and A method of washing once or twice or more with a solvent selected from alcohol or the like, followed by neutralization, washing with water, filtration and drying.

Moreover, in the post-processing method as illustrated in said (1)-(3), drying of polyarylene sulfide resin may be performed in vacuum, and may be performed in air or in an inert gas atmosphere like nitrogen. It is also possible to oxidatively crosslink polyarylene sulfide resin by performing heat treatment in an oxidizing atmosphere in an oxygen concentration of 5 to 30% by volume or under reduced pressure conditions.

The reaction which polyarylene sulfide resin produces|generates by melt polymerization is illustrated below.

Reaction formulas (1) to (5) are, for example, when diphenyldisulfide having a substituent R containing a group represented by the general formulas (a), (b) or (c) is used as a polymerization inhibitor, This is an example of a reaction produced by polyphenylene sulfide. Reaction formula (1) is a reaction in which -S-S- bond in a polymerization inhibitor radically cleaves under melting temperature. In Reaction Formula (2), the sulfur radical generated in Reaction Formula (1) attacks a carbon atom adjacent to the terminal iodine atom of the growing main chain, and the iodine atom is released, so that polymerization is stopped, and a substituent R is introduced at the end of the main chain is a reaction Reaction formula (3) is a reaction in which the disulfide bond which originates in a raw material (single sulfur) and exists in the main chain of polyarylene sulfide resin radically cleaves under a melting temperature. Reaction formula (4) is a reaction in which polymerization is stopped and a substituent R is introduced into the terminal of the main chain by recombination between the sulfur radical generated in the reaction formula (3) and the sulfur radical generated in the reaction formula (1). The detached iodine atom is in a free state (iodine radical), or when iodine radicals recombine as shown in Reaction Formula (5), iodine molecules are formed.

The reaction product containing polyarylene sulfide resin obtained by melt polymerization contains the iodine atom derived from a raw material. Therefore, polyarylene sulfide resin is the state of the mixture containing an iodine atom normally, and is used for preparation of the resin composition for spinning, etc. The density|concentration of the iodine atom in the said mixture is the range of 0.01-10000 ppm with respect to polyarylene sulfide resin, for example, Preferably it is the range of 10-5000 ppm. It is also possible to suppress the iodine atom concentration to a low level by using the sublimation property of the iodine molecules. It is also possible to further remove iodine atoms below the detection limit, but it is not practical in view of productivity. The detection limit is, for example, about 0.01 ppm. Since the polyarylene sulfide resin of the present embodiment obtained by melt polymerization or the reaction product containing the same contains an iodine atom, for example, solution polymerization of a dichloro aromatic compound such as the Phillips method in an organic polar solvent. It can be clearly distinguished from the polyarylene sulfide obtained by the method.

As is also understood from the above reaction formula, the polyarylene sulfide resin obtained by melt polymerization is a main chain mainly composed of an arylene sulfide unit consisting of an aromatic ring derived from a diiodo aromatic compound and a sulfur atom directly bonded thereto; It contains a predetermined substituent R bonded to the terminal of the main chain. The predetermined substituent R is bonded to the aromatic ring at the terminal of the main chain directly or through a partial structure derived from a polymerization inhibitor.

The polyphenylene sulfide resin as the polyarylene sulfide resin according to one embodiment is, for example, the following general formula (10):

It has a main chain including a repeating unit (arylene sulfide unit) represented by The repeating unit represented by formula (10) has the following formula (10a) bonded at the para position:

A repeating unit represented by, and the following formula (10b) coupled at a meta position:

It is more preferable that it is a repeating unit represented by Among these, the repeating unit couple|bonded at the para position represented by Formula (10a) is preferable from the point of heat resistance and crystallinity of resin.

Polyphenylene sulfide resin according to one embodiment, the following general formula (11):

(Wherein, R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group)

It may include a repeating unit having a substituent as a side chain bonded to the aromatic ring represented by . However, it is preferable that polyphenylene sulfide resin does not contain the repeating unit of General formula (11) substantially from a viewpoint of the fall of crystallinity and heat resistance. More specifically, the proportion of the repeating unit represented by the formula (11) is preferably 2% by mass or less with respect to the total of the repeating unit represented by the formula (10) and the repeating unit represented by the formula (11). , More preferably, it is 0.2 mass % or less.

Although the polyarylene sulfide resin of this embodiment is mainly comprised by the said arylene sulfide unit, the following formula (20) derived from the single-piece sulfur of a raw material normally:

A structural unit according to a disulfide bond represented by is also included in the main chain. From the viewpoint of heat resistance and mechanical strength, the proportion of the structural unit represented by the formula (20) is preferably 2.9% by mass or less with respect to the total of the arylene sulfide unit and the structural site represented by the formula (20). range, more preferably 1.2 mass % or less.

Mw/Mtop of polyarylene sulfide resin which concerns on this embodiment becomes like this. Preferably it is the range of 0.80-1.70, More preferably, it is the range of 0.90-1.30. By making Mw/Mtop into such a range, the workability of polyarylene sulfide resin can be improved and favorable cavity balance can be provided. In this specification, Mw represents the weight average molecular weight measured by gel permeation chromatography, and Mtop represents the average molecular weight (peak molecular weight) of the point at which the detection intensity of the chromatogram obtained by the same measurement becomes maximum. Mw/Mtop represents the distribution of the molecular weight of the measurement target, and usually, when this value is close to 1, it indicates that the distribution of molecular weight is narrow, and as this value increases, it indicates that the distribution of molecular weight is wide. In addition, the measurement conditions of gel permeation chromatography are set as the measurement conditions similar to the Example of this specification. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw/Mtop.

The weight average molecular weight of the polyarylene sulfide resin according to the present embodiment is not particularly limited as long as the effects of the present invention are not impaired, but the lower limit thereof is preferably 28,000 or more in terms of excellent mechanical strength, and is in the range of 30,000 or more. more preferably. On the other hand, the upper limit is preferably in the range of 100,000 or less, more preferably in the range of 60,000 or less, and most preferably in the range of 55,000 or less in terms of providing better cavity balance. Furthermore, from the viewpoint of being excellent in mechanical strength and providing good cavity balance, a polyarylene sulfide resin in the range of 28,000 to 60,000, more preferably a polyarylene sulfide resin in the range of 30,000 to 55,000; Together, the weight average molecular weight may use polyarylene sulfide resin in the range of more than 60,000 and 100,000 or less.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, more preferably in the range of 1.00 to 1.70. By making the non-Newtonian index into such a range, the workability of polyarylene sulfide resin can be improved, and favorable cavity balance can be provided. In the present specification, the non-Newtonian index refers to an index that satisfies the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300°C. The non-Newtonian index may be an index relating to the molecular weight of a measurement target or a molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 1, it shows that the molecular structure of resin is linear, and as this value becomes large, it shows that many branched and crosslinked structures are contained.

D=α×S ⁿ

(Wherein, D represents the shear rate, S represents the shear stress, α represents the constant, and n represents the non-Newtonian index)

Polyarylene sulfide resin having Mw/Mtop and non-Newtonian index in the specific range described above is, for example, a diiodo aromatic compound, a single sulfur, a polymerization inhibitor, a diiodo aromatic compound, a single sulfur And in the method of reacting (solution polymerization) in a molten mixture containing a polymerization inhibitor, it is possible to obtain by making this polyarylene sulfide resin high molecular weight to some extent.

Melting|fusing point of polyarylene sulfide resin becomes like this. Preferably it is the range of 250-300 degreeC, More preferably, it is the range of 265-300 degreeC. Melt viscosity (V6) in 300 degreeC of polyarylene sulfide resin becomes like this. Preferably it is the range of 1-2000 [Pa*s], More preferably, it is the range of 5-1700 [Pa*s]. Here, the melt viscosity (V6) was measured using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice whose ratio of orifice length to orifice diameter (orifice length/orifice diameter) was 10/1 for 6 minutes It means the melt viscosity after holding.

As a silicone compound used for this embodiment, the polyorganosiloxane represented by the following general formula (I) which has a siloxane bond in a principal chain is preferable.

R ³⁰ -[Si(R ³¹ ) ₂ -O]n ¹ -R ³² (I)

(Wherein, R ³⁰ , R ³¹ and R ³² each independently represent a hydrogen atom or an organic group, and n ¹ is an integer of 2 or more)

^{Among these, polydimethylsiloxane in which R 30} , R ³¹ and R ³² in the general formula (1) are all methyl groups is particularly preferable, and those in which a part of the methyl groups of the polydimethylsiloxane are substituted with hydrogen atoms or other substituents desirable.

Examples of the other substituent include an alkyl group having 2 or more carbon atoms, an aryl group, a halogenated alkyl group, a silylalkyl group, a polyoxyalkylene group, and a reactive functional group. It is selectable.

Examples of the alkyl group having 2 or more carbon atoms include an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. As an aryl group, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned, for example.

Examples of the halogenated alkyl group include a fluoropropyl group and a chloropropyl group.

The silylalkyl group is represented by the following general formula (II) as a typical specific example thereof.

-(CH ₂ )n ² -Si(OCH ₃ ) ₃ (II)

(wherein n ² is an integer greater than or equal to 1)

Specific examples of the polyoxyalkylene group include those represented by the following general formula (III).

-[CH ₂ ]kO-[C ₂ H ₄ O] l-[C ₃ H ₆ O] mR ³³ (III)

(Wherein, k, l and m are each independently 0 or a positive integer, and l and m simultaneously take non-zero integers. R ³³ is a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group, at least one substituent selected from the group consisting of a silylalkyl group and a reactive functional group to be described later)

It is preferable that a silicone compound has a reactive functional group. Specific examples of the reactive functional group include an epoxy group, an amino group, a mercapto group, a vinyl group, a carboxy group, a hydroxyl group, an isocyanate group, an amide group, an acyl group, a nitrile group, and an acid anhydride group. These reactive functional groups may be directly couple|bonded with the main chain, or may couple|bond with the terminal of organic groups, such as an alkylene group couple|bonded with the main chain, polyoxyalkylene group. Among them, a carboxy group, a hydroxyl group, an epoxy group and an amino group are particularly preferable, and an epoxy group and an amino group are more preferable.

The silicone compound exhibits an effect of improving durability with respect to the electrolyte solution by being uniformly dispersed in the resin composition. Oily ones in the range of 80,000 mPa·s are suitable. Moreover, in order to disperse|distribute a silicone compound uniformly in the resin composition of this embodiment, it is preferable to use what supported the silicone compound on inorganic powder, such as silica.

When a reactive functional group is contained in a silicone compound, dispersion|distribution of the silicone compound to a resin composition will be made favorable, Therefore, the improvement of impact resistance can be aimed at. Moreover, it is preferable also from the point which has the effect of suppressing the so-called bleed-out which a silicone compound seeps on the surface of a molded article.

The content rate of the reactive functional group in the silicone compound is preferably 400 g/equivalent (hereinafter abbreviated as "g/eq") or more from the viewpoint of imparting a more preferable effect to imparting impact resistance and toughness, and mixing 50,000 g/eq or less is preferable at the point of easiness.

Moreover, it is preferable that the compounding quantity of a silicone compound is 0.1-10 mass parts with respect to a total of 100 mass parts of polyarylene sulfide resin and a silicone compound, It is more preferable that it is 0.3-5 mass parts, It is more preferable that it is 0.5-3 mass parts do.

You may mix|blend a silane compound with the resin composition for gaskets of this embodiment. As a silane compound, aminoalkoxy silane, an epoxy alkoxy silane, vinyl alkoxy silane, etc. are mentioned, for example. These silane compounds may be used independently and may use 2 or more types together.

As the aminoalkoxysilane, any silane compound having one or more amino groups and two or more alkoxy groups in one molecule can be used, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-Aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxy Silane, N-β (aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N -phenyl-γ-aminopropyltrimethoxysilane, etc. are mentioned.

As the epoxyalkoxysilane, any silane compound having one or more epoxy groups and two or more alkoxy groups in one molecule can be used, for example, γ-glycidoxypropyltrimethoxysilane, β-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc. are mentioned.

As the vinyl alkoxysilane, any silane compound having one or more vinyl groups and two or more alkoxy groups in one molecule can be used, for example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methyl and ethoxyethoxy) silane.

In this embodiment, in addition to each said component, you may add a fibrous reinforcing material or an inorganic filler in the range which does not impair the effect shown by this invention.

Examples of the fibrous reinforcing material include glass fibers, PAN-based or pitch-based carbon fibers, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, aluminum borate fibers, potassium titanate fibers, and stainless steel. , inorganic fibrous substances of metals such as aluminum, titanium, copper and pearls, and organic fibrous substances such as aramid fibers.

Examples of the inorganic filler include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbesto, alumina silicate, zeolite, and pyrophyllite, calcium carbonate, magnesium carbonate, dolomite, and the like. of carbonate, calcium sulfate, sulfates such as barium sulfate, metal oxides such as alumina, magnesium oxide, silica, zirconia, titania, iron oxide, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, and the like. These fibrous reinforcing materials and inorganic fillers may be used individually or in combination of 2 or more types.

Moreover, in the resin composition for gaskets of this embodiment, in the range which does not impair the effect shown by this invention, antioxidant, a stabilizer, a processing heat stabilizer, a plasticizer, a mold release agent, a coloring agent, a lubricant, An appropriate amount of a weathering stabilizer, foaming agent, rust preventive agent and wax may be blended.

Furthermore, you may mix|blend other resin components suitably with the resin composition for gaskets of this embodiment according to the characteristic calculated|required. Examples of the resin component usable herein include ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth)acrylonitrile, and the like. homopolymer or copolymer of monomers, polyurethane, polybutylene terephthalate, polyester such as polyethylene terephthalate, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyphenylene ether, polyether Homopolymers such as ketones, polyetheretherketones, polyimides, polyamideimides, polyetherimides, silicone resins, epoxy resins, phenoxy resins, liquid crystal polymers, polyarylethers, random copolymers or block copolymers, graft copolymers and the like.

Specifically, as a method for producing the resin composition for a gasket of the present embodiment, a silicone compound, a polyarylene sulfide resin, and other blending components to be blended as necessary are uniformly mixed with a tumbler, a Henschel mixer, or the like, and then , the mixture is put into a twin-screw extruder, and the ratio of the discharge amount (kg/hr) of the resin component and the screw rotation speed (rpm) (discharge amount/screw rotation speed) is in the range of 0.02 to 0.2 (kg/hr rpm) The method of melt-kneading under the conditions used is mentioned.

Regarding the above-described manufacturing method, if described in more detail, a method of introducing each of the above-mentioned components into a twin-screw extruder, and melt-kneading under the temperature conditions of a set temperature of 330°C and a resin temperature of about 350°C is mentioned. At this time, the discharge amount of the resin component is in the range of 5 to 50 kg/hr at the rotation speed of 250 rpm. Especially, it is preferable that it is 20-35 kg/hr from a dispersible point. Therefore, it is preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of a resin component and screw rotation speed (rpm) is especially 0.08-0.14 (kg/hr·rpm).

The resin composition for gaskets melt-kneaded in this way is usually cut into pellets. Furthermore, by supplying the obtained pellets to a molding machine and melt-molding, the molded object of the target shape is finally obtained.

Examples of the melt-molding method include injection molding, extrusion molding, and compression molding. Among them, injection molding is particularly preferable as a method for molding the gasket for a secondary battery.

The resin composition for gaskets of the present embodiment is, for example, a secondary battery used in electric equipment applications such as notebook PCs, mobile phones, and video cameras, or in-vehicle applications such as hybrid vehicles (HV) and electric vehicles (EV). , especially for gaskets for high-capacity lithium ion secondary batteries, and the like.

[Example]

Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to these Examples.

1. Polyphenylene sulfide resin (PPS resin)

1-1. Synthesis of PPS-1 to 5

(Synthesis Example 1)

p-diiodobenzene (Tokyo Chemical Co., Ltd., p-diiodobenzene purity 98.0% or more) 300.0 g, solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) 27.00 g, 4 2.0 g of ,4'-dithiobisbenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobisbenzoic acid, Technical Grade) was heated at 180° C. in a nitrogen atmosphere to dissolve and mix them. Next, it heated up at 220 degreeC and pressure-reduced to 26.6 kPa absolute. Melt polymerization was performed for 8 hours, heating the molten mixture obtained by changing the temperature and pressure step by step so that the inside of the system was 320°C and the absolute pressure was 133 Pa. After completion of the reaction, 200 g of NMP was added, and the resulting solution was filtered by heating and stirring at 220°C. NMP 320g was added to the melt|dissolution after filtration, and cake washing|cleaning filtration was performed. 1 L of ion-exchange water was added to the cake containing the obtained NMP, and it stirred for 10 minutes at 200 degreeC in an autoclave. Next, the cake was filtered, and 1 L of 70 degreeC ion-exchange water was added to the cake after filtration, and cake washing|cleaning was performed. 1 L of ion-exchanged water was added to the obtained water-containing cake, and it stirred for 10 minutes. Next, the cake was filtered, and 1 L of 70 degreeC ion-exchange water was added to the cake after filtration, and cake washing|cleaning was performed. After repeating this operation once more, the cake was dried at 120 degreeC for 4 hours, and 91 g of PPS resins were obtained.

(Synthesis Example 2)

91 g of PPS resin was obtained in the same manner as in Synthesis Example 1 except that "2-iodoaniline (manufactured by Tokyo Chemical Co., Ltd.)" was used instead of "4,4'-dithiobisbenzoic acid".

(Synthesis Example 3)

91 g of PPS resin was obtained in the same manner as in Synthesis Example 1 except that "diphenyl disulfide (Sumitomo Chemical Co., Ltd., DPDS)" was used instead of "4,4'-dithiobisbenzoic acid".

(Synthesis Example 4)

300.0 g of p-diiodobenzene (manufactured by Tokyo Chemical Co., Ltd., purity of 98.0% or more of p-diiodobenzene), 29.15 g of solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) and 1.48 g of 4-iodobiphenyl (manufactured by Tokyo Chemical Co., Ltd.) was heated at 180°C in a nitrogen atmosphere to dissolve and mix them. Next, the temperature was raised to 220 ° C, the pressure was reduced to 46.7 kPa, and the temperature and pressure were changed stepwise so that the inside of the system was 320 ° C. and the absolute pressure was 133 Pa. While heating the obtained molten mixture, melt polymerization was performed for 8 hours. After completion of the reaction, 200 g of NMP was added, and the resulting solution was filtered by heating and stirring at 220°C. NMP 320g was added to the lysate after filtration, and cake washing-filtration was performed. 1 L of ion-exchange water was added to the cake containing the obtained NMP, and it stirred for 10 minutes at 200 degreeC in the autoclave. Next, the cake was filtered, and 1 L of 70 degreeC ion-exchange water was added to the cake after filtration, and cake washing|cleaning was performed. 1 L of ion-exchange water was added to the obtained water-containing cake, and it stirred for 10 minutes. Next, the cake was filtered, and 1 L of 70 degreeC ion-exchange water was added to the cake after filtration, and cake washing|cleaning was performed. After repeating this operation once more, the cake was dried at 120 degreeC for 4 hours, and 91 g of PPS resins were obtained.

(comparative synthesis example)

600 g of NMP and 336.3 g (2.0 mol) of sodium sulfide pentahydrate were added, and the water-NMP mixture was distilled off by raising the temperature to 200° C. under a nitrogen atmosphere. Next, a solution of 292.53 g of p-dichlorobenzene and 1.62 g of 2,5-dichloroaniline dissolved in 230 g of NMP was added to this system, and reacted at 220° C. for 5 hours and further at 240° C. for 2 hours under a nitrogen atmosphere. After cooling the reaction vessel, the contents were taken out, a portion was sampled, and unreacted 2,5-dichloroaniline was quantified with a gas chromatograph. In addition, the remaining slurry was washed several times with hot water, and the polymer cake was separated by filtration. This cake was dried under reduced pressure at 80°C to obtain a powdery PPS resin. When the infrared absorption spectrum was measured, the absorption spectrum which seems to originate in the amino group was observed in the vicinity of ^{3380 cm -1.}

1-2. melt viscosity

The PPS resin Shimadzu assay Saku syoje flow tester, using a CFT-500C, 300 ℃, load: from ^{1.96 × 10 6 ㎩, L /} D = 10/1, to measure the melt viscosity after holding for 6 minutes.

1-3. Non-Newtonian exponent

The PPS resin was used as a capillary rheometer and the shear stress with respect to a shear rate of ^{100 to 1000 (sec -1} ) was measured using a die having a diameter of 1 mm and a length of 40 mm under the condition of a temperature of 300 ° C. It is a value calculated from the logarithmic plotted slope.

1-4. Mw and Mw/Mtop (molecular weight distribution)

The weight average molecular weight and peak molecular weight of PPS resin were measured by the following measurement conditions using gel permeation chromatography. Mw/Mtop was computed from the obtained Mw and Mtop. Six types of monodisperse polystyrene were used for calibration.

Apparatus: Ultra-high temperature polymer molecular weight distribution measuring device (“SSC-7000” manufactured by Sens Chemical Co., Ltd.)

Column: UT-805L (manufactured by Showa Denko Co., Ltd.)

Column temperature: 210℃

Solvent: 1-chloronaphthalene

Measurement method: UV detector (360nm)

Table 1 summarizes the characteristics of the synthesized PPS-1 to 5.

[Table 1]

2. Polyphenylene sulfide resin composition (PPS compound)

2-1. Raw material

In order to prepare the PPS resin composition, the following silicone compounds were prepared.

Si-1: Silicone powder (Toray Dow Corning Co., Ltd., "Treefil F-202", powder in which 60 mass% of silicone oil (viscosity (25°C) 62 Pa·s) is supported on silica)

-Si-2: silicone containing amino group (manufactured by Shin-Etsu Chemical Co., Ltd., "KF-868")

2-2. production of compounds

After uniformly mixing each raw material using a tumbler with the compounding composition shown in Table 2, melt kneading at 300 ° C. using a twin-screw kneading extruder (manufactured by Toshibagi Kai Co., Ltd., "TEM-35B"), A pelletized compound was obtained.

3. Evaluation

3-1. Tensile strength and tensile elongation

From the obtained compound, the molded article for evaluation injection molded into ASTM No. 4 dumbbell shape was measured for tensile elongation at break using "Autograph AG-5000C" manufactured by Shimadzu Corporation in accordance with ASTM D638.

3-2. compressive stress relaxation test

The resin composition pellets were molded using an injection molding machine, and a flat plate having a length of 8 mm × width 8 mm × thickness 3 mm was molded by an injection molding machine, and a test piece for relaxation of compressive stress as shown in FIG. 1 was produced. Using this test piece, compressive stress relaxation was measured under 10% strain (temperature conditions: 23°C and 60°C) by "Autograph AG-50KNX" manufactured by Shimadzu Corporation equipped with a thermostat equipped with a thermostat, after 100 hours The compressive stress was obtained.

3-3. Assessment of confidentiality

The resin composition pellets were shape|molded using the injection molding machine, and the shape produced the box-shaped molded article of length 8mm x width 8mm x height 10mm, and thickness 0.8mm. Next, an electrolyte solution (1 mol/L LiPF6/ethylene carbonate (EC):dimethyl carbonate (DMC) (volume 1:1 mixed solution) solution, manufactured by Kishida Chemical Co., Ltd.) was put into this box-shaped molded article, and compressed A sample for airtightness test sealed with a constant stress (under 10% strain) with a flat plate having a length of 8 mm × width 8 mm × thickness 3 mm used in the stress relaxation test was prepared. This was left to stand under 60 degreeC dry heat for 100 hours, and the leak degree of a liquid was confirmed. In addition, the evaluation result was displayed as follows.

○: No leakage of liquid after 100 hours

×: leakage of liquid occurs after 100 hours

3-4. cavity balance

Using a washer mold having 40 cavities, the PPS compound was injection molded under the minimum molding conditions in which the cavity (C1) closest to the primary spool was completely filled. The molding conditions were a 75-ton molding machine, a cylinder temperature of 320°C, a mold temperature of 140°C, and no holding pressure.

After molding, the degree of filling of the cavity (C10) furthest from the primary spool on the same runner as the cavity (C1) was compared. The filling degree (mass %) was calculated|required from the mass ratio of the molded article of the cavity C10 with respect to the molded article of the cavity C1. It can be said that the cavity balance is excellent, so that the filling degree of the cavity C10 is high. Based on the filling degree, the cavity balance of each composition was judged on the following reference|standard.

AA: 100 to 90 mass %

A: 89 to 80 mass %

B: 79 to 70 mass %

C: 69-60 mass %

D: 59% by mass or less

3-5. amount of gas generated

Using a gas chromatograph mass spectrometer, a predetermined amount of the sample was heated at 325° C. for 15 minutes for the PPS resin alone and the PPS compound, and the amount of gas generated at that time was quantified as mass%.

[Table 2]

As is clear from the results shown in Table 2, the resin composition produced in Examples has excellent cavity balance, high mechanical strength, and can form molded articles excellent in airtightness. When used as a gasket, it is necessary for a secondary battery confidentiality can be maintained.

Claims (7)

A resin composition for a gasket used in a secondary battery consisting of a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte,
It contains a polyarylene sulfide resin and a silicone compound,
The polyarylene sulfide resin reacts with a diiodo aromatic compound, single sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the single sulfur compound and the polymerization inhibitor. A resin composition for gaskets obtainable by a method comprising: The method of claim 1,
The resin composition for gaskets in which the said polyarylene sulfide resin has at least 1 sort(s) of group selected from the group which consists of a salt of the hydroxyl group, amino group, carboxy group, and carboxyl group derived from the said polymerization inhibitor. 3. The method of claim 1 or 2,
The said polyarylene sulfide resin has a non-Newtonian index of 0.95-1.75 in 300 degreeC, and Mw/Mtop of 0.80-1.70,
wherein Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively. The gasket for secondary batteries which consists of the resin composition for gaskets in any one of Claims 1-3. A method for producing a resin composition for a gasket used in a secondary battery comprising a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte, the method comprising:
having a process of mixing a polyarylene sulfide resin and a silicone compound,
The polyarylene sulfide resin comprises reacting a diiodo aromatic compound, single sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the single sulfur and the polymerization inhibitor The manufacturing method of the resin composition for gaskets which is obtainable by the method. 6. The method of claim 5,
The manufacturing method of the resin composition for gaskets in which the said polyarylene sulfide resin has at least 1 sort(s) of group selected from the group which consists of a salt of the hydroxyl group, amino group, carboxy group, and carboxyl group derived from the said polymerization inhibitor. 7. The method according to claim 5 or 6,
The said polyarylene sulfide resin has a non-Newtonian index of 0.95-1.75 in 300 degreeC, and Mw/Mtop of 0.80-1.70,
Wherein Mw and Mtop are a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography, respectively.

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