TW202204480A - Resin composition for gasket and gasket for secondary battery comprising the same - Google Patents

Abstract

The present invention relates to a novel polyarylene sulfide resin composition for a gasket and to a gasket for a secondary battery comprising the same. The resin composition for a gasket of the embodiment may have a low amount of outgassing, excellent airtightness, cavity balance, tensile strength, tensile elongation, and/or crystallinity.

Description

Resin composition for gasket and gasket for secondary battery containing the same

Field of Invention

The present invention relates to a resin composition for a gasket and a secondary battery gasket including the same.

Background of the Invention

As a power source for driving a portable device, sealed secondary batteries such as aqueous electrolyte secondary batteries typified by high-capacity alkaline storage batteries and non-aqueous secondary batteries typified by lithium ion secondary batteries are widely used.

In general, a sealed secondary battery includes: a set of electrode plates including an anode plate, a cathode plate, and a separator disposed between the anode and cathode plates; and an electrolyte solution for immersing the set of electrode plates, the The electrolyte solution is contained in a battery case (external body) provided with an opening, wherein the opening of the battery case is sealed by the sealing body. For example, in such a sealed secondary battery, a gasket is provided at the point of contact between the electrical connection between the anode plate and the anode terminal or between the electrical connection between the cathode plate and the cathode terminal to prevent the occurrence of damage between the pair of terminals short circuit or prevent electrolyte leakage.

A technique using a polyarylene sulfide resin as a material of such a gasket has been reported (see Patent Document 1). Polyphenylene sulfide is the only polyarylene sulfide currently sold on a commercial scale. The production methods thereof are a solution polymerization method in which p-dichlorobenzene and sodium sulfide are polymerized as raw materials in an N-methylpyrrolidone solvent (see Patent Document 1); and a melt polymerization method in which a diiodoaromatic compound and The sulfur compound as a raw material is polymerized at high temperature without using a solvent.

It is known that the heat resistance, flame resistance and durability of polyphenylene sulfide resins produced by solution polymerization are adversely affected by large outgassing due to the use of solvents and chlorine in the raw materials.

The polyphenylene sulfide resin produced by the melt polymerization method produces an improved effect, making it an excellent productivity and cost structure because it does not use a solvent, has a small outgassing amount, and has the advantages of Excellent corrosion resistance. However, due to its low reactivity with processing additives due to the non-polarity of the end groups of the resin, it is difficult to modify to have desired characteristics, resulting in limited use and application. Another limitation is that disulfide bonds derived from sulfur compounds used as raw materials act as weak structures in the resin, resulting in insufficient mechanical strength.

Such gaskets for secondary batteries must basically have chemical resistance against electrolytes and excellent air tightness. In addition, the gasket must have excellent mechanical strength so that it can maintain airtightness even when the secondary battery is subjected to mechanical shock or the internal pressure is increased (gas is generated when the solvent in the secondary battery is vaporized or decomposed by heating Airtightness can also be maintained in an environment with .

Meanwhile, a molded article such as a gasket can be manufactured by injection molding a resin using a mold having a plurality of cavities so as to simultaneously manufacture a plurality of molded articles. In such injection molding, if the molding material is insufficiently filled in some cavities, resulting in molding defects, it reduces productivity. Therefore, the resin used for the gasket or the like must have good cavity balance.

As a result of thorough research to solve this problem, the present inventors have found that if a gasket is manufactured using a polyarylene sulfide resin post-treated with a compatibilizer, the cavity balance can be improved while maintaining good airtightness and mechanical strength . In addition, it has been found that blending a polyarylene sulfide resin prepared by solution polymerization with a polyarylene sulfide resin prepared by melt polymerization can produce mats with good cavity balance while maintaining excellent air tightness and mechanical strength sheet, whereby the present invention has been completed. [Prior Art Literature] [Patent Literature] (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei 8-321287 (Patent Document 2) US Patent No. 2,513,188

Summary of Invention Technical Problem

An object of the present invention is to provide a novel polyarylene sulfide resin composition for a gasket and a secondary battery gasket including the same. problem solution

The present invention provides a resin composition for a gasket, comprising: a post-treated first polyarylene sulfide resin, wherein end groups derived from a compatibilizer are introduced into a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor in the melt-polymerized first polyarylene sulfide resin; and at least one additive selected from the group consisting of glass fibers, elastomers and thermal stabilizers.

In addition, the present invention provides a resin composition for a gasket, comprising: a first polyarylene sulfide resin melt-polymerized from a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; A second polyarylene sulfide resin that undergoes solution polymerization with a second sulfur compound; and at least one additive selected from the group consisting of glass fibers, elastomers and thermal stabilizers, wherein the first polyarylene sulfide resin and the second poly The second polyarylene sulfide resin is used in an amount of 0.0001 to 30% by weight based on the total weight of the arylene sulfide resin.

In addition, the present invention provides a resin composition for a gasket, comprising: a post-treated first polyarylene sulfide resin, wherein an end group derived from a compatibilizer is introduced into a diiodo aromatic compound, a first polyarylene sulfide resin In the first polyarylene sulfide resin melt-polymerized by a sulfur compound and a polymerization inhibitor; a second polyarylene sulfide resin subjected to solution polymerization by a dihalogen aromatic compound and a second sulfur compound; and at least one selected from the group consisting of glass fiber, elastic The additive of the group consisting of a body and a thermal stabilizer, wherein the second polyarylene sulfide resin is used in an amount of 0.0001 to 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin .

In addition, the present invention provides a gasket for a secondary battery comprising a molded article obtained from the resin composition for the gasket.

In addition, the present invention provides a secondary battery comprising: an outer body having an opening; a sealing body for sealing the opening of the outer body; an anode plate, a cathode plate, and an electrolyte provided in the outer body; A separator between the cathode plates; an anode terminal electrically connected to the anode plate; a cathode terminal electrically connected to the cathode plate; and a secondary battery gasket in contact with the anode terminal or the cathode terminal. Advantageous Effects of the Invention

The polyarylene sulfide resin composition for gaskets of the present invention can reduce outgassing and have excellent air tightness, cavity balance, tensile strength, tensile elongation and/or crystallinity.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, the present invention is described in detail. The present invention is not limited to the disclosure given below, but can be modified into various forms as long as the gist of the present invention is not changed. [ Post-treated polyarylene sulfide resin composition ]

According to one embodiment, there is provided a resin composition for a gasket (hereinafter referred to as a post-treated first polyarylene sulfide resin composition), comprising: a post-treated first polyarylene sulfide resin, wherein end groups derived from the compatibilizer are introduced into the first polyarylene sulfide resin melt polymerized from the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor; and an additive.

According to another embodiment, there is provided a method for preparing a gasket resin composition, comprising: preparing a first polyarylene sulfide resin melt-polymerized from a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; mixing the first polyarylene sulfide resin with additives; and post-processing the first polyarylene sulfide resin with a compatibilizer. The first polyarylene sulfide resin

The first polyarylene sulfide resin can be prepared by melt-polymerizing a composition including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor.

Diiodoaromatic compounds refer to compounds having an aromatic ring and two iodine atoms directly bonded thereto. The diiodoaromatic compound may be at least one selected from the group consisting of diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododi Phenyl ether and diiododiphenyl, but not limited thereto.

The aromatic ring in the diiodoaromatic compound may be substituted with at least one substituent selected from the group consisting of halo, phenyl, hydroxy, nitro, amine, alkoxy having 1 to 6 carbon atoms , carboxyl, carboxylate, aryl and aryl ketones, excluding iodo. When the aromatic ring in the diiodo aromatic compound is substituted with a substituent, from the viewpoint of resin crystallinity and heat resistance, the diiodo aromatic compound having an unsubstituted aromatic ring has a substituent substituted The diiodo aromatic compound of the aromatic ring may be 0.0001 to 5 wt % or 0.001 to 1 wt %. Although the substitution positions of the two iodine groups present in the diiodoaromatic compound are not particularly limited, the two substitution positions may be located away from each other in the molecule and may be the para-position or the 4,4'-position.

The diiodo aromatic compound may be 0.5 to 2.0 mol, 0.55 to 1.9 mol, 0.6 to 1.8 mol, 0.65 to 1.7 mol, 0.7 to 1.6 mol, 0.75 to 1.5 mol relative to 1 mol of the first sulfur compound ear or in an amount of 0.8 to 1.4 moles. The diiodoaromatic compound can be, for example, p-diiodobenzene.

The first sulfur compound may be elemental sulfur. Elemental sulfur refers to compounds composed of sulfur atoms. The elemental sulfur may be at least one selected from the group consisting of S ₈ , S ₆ , S ₄ and S ₂ , and specifically, it may be a mixture including commercially available S ₈ and S ₆ , but it is not limited thereto . The purity, form and particle size of elemental sulfur are not particularly limited. For example, elemental sulfur may be in solid particulate or powder form at room temperature (23°C). In addition, the elemental sulfur may have a particle size of 0.001 to 10 mm, 0.01 to 5 mm, or 0.01 to 3 mm, but it is not limited thereto.

The polymerization inhibitor can be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction of the first polyarylene sulfide resin. The polymerization inhibitor may be a compound whose at least one functional group selected from the group consisting of -OR, -SR, -COOR, -NHR, _-SO3R , -NHCOR and Similar groups, wherein R can each independently be a hydrogen group, a metal cation such as sodium or lithium, a halo group, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. The polymerization inhibitor may contain the functional group and the functional group may be formed by terminating the polymerization reaction or the like. In addition, the polymerization inhibitor may be a compound that does not contain the functional group. Specifically, it may be at least one compound selected from the group consisting of diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole , N-cyclohexyl-2-benzothiazole sulfenamide, 2-(morpholinylthio) benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide amine.

In addition, the polymerization inhibitor may be one or more of the compounds represented by the following formulae 1 to 3, and specifically, it may be the compound represented by the formula 1. [Formula 1]

X ¹ and X ² are each independently selected from the group consisting of hydrogen, halo, alkyl having 1 to 3 carbon atoms, substituted or unsubstituted phenyl, -OA ¹ , -SA ² , -COOA ³ , -NA ⁴ A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ , wherein A ¹ to A ⁷ are each independently selected from the group consisting of: hydrogen, sodium cation, lithium cation, having 1 to 3 A substituted or unsubstituted alkyl group of carbon atoms, and a substituted or unsubstituted phenyl group, Z ¹ to Z ⁴ are each independently selected from the group consisting of: a hydrogen group, a group having 1 or 2 carbon atoms substituted or unsubstituted alkyl, and substituted or unsubstituted alkenyl having 1 or 2 carbon atoms, and m ¹ and m ² are each independently an integer from 1 to 3.

When Z ¹ and Z ² are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring. In addition, when Z ³ and Z ⁴ are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring.

When m ¹ or m ² is 2 or more, two or more X ¹ or X ² bonded to one aromatic ring may be the same or different from each other. Additionally, Z ¹ and Z ³ may be the same or different from each other, and Z ² and Z ⁴ may be the same or different from each other.

The substituted phenyl group in X ¹ or X ² may have a substituent of -SH or -SS-Ph. In addition, the substituted alkyl group and the substituted phenyl group having 1 to 3 carbon atoms in A ¹ to A ⁷ may each independently have a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group.

Z ¹ and Z ² can be bonded to two adjacent carbon atoms, and Z ³ and Z ⁴ can be bonded to two adjacent carbon atoms.

In addition, at least one or two or more of Z ¹ to Z ⁴ may not be a hydrogen group. Additionally, at least one of X ¹ and X ² may be selected from the group consisting of -OA ¹ , -SA ² , -COOA ³ , -NA ⁴ A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ . In addition, for example, when X ¹ and X ² are both hydrogen groups, at least one of the combination of Z ¹ and Z ² or the combination of Z ³ and Z ⁴ may be connected to each other to form a benzene ring. [Formula 2]

X ³ to X ⁶ are each independently selected from the group consisting of a hydrogen group, a halogen group, an alkyl group having 1 to 5 carbon atoms, -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , wherein A ⁸ to A ¹⁴ are each independently selected from the group consisting of hydrogen radicals, sodium cations, lithium cations, and alkyl groups having 1 to 3 carbon atoms, and R ¹ to R ⁴ is each independently an alkylene group or an alkoxy group having 1 to 5 carbon atoms.

At least one of X ³ to X ⁶ may be selected from the group consisting of -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ . In addition, at least one of X ³ to X ⁶ may be -SA ⁹ , wherein A ⁹ is a hydrogen group. [Formula 3]

X ⁷ to X ¹² are each independently selected from the group consisting of hydrogen, halogen, alkyl having 1 to 5 carbon atoms, -OA ¹⁵ , -SA ¹⁶ , -COOA ¹⁷ , -NA ¹⁸ A ¹⁹ , -SO ₃ A ²⁰ and -NHCOA ²¹ , wherein A ¹⁵ to A ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ is each independently an alkylene group having 1 to 5 carbon atoms.

In addition, the polymerization inhibitor may be used in an amount of 0.0001 to 0.1 mol, 0.0002 to 0.08 mol, 0.0005 to 0.05 mol, or 0.001 to 0.05 mol relative to 1 mol of the first sulfur compound.

Meanwhile, a catalyst may be additionally used in the melt polymerization. The catalyst may be, for example, a nitrobenzene-based catalyst. Specifically, it may be one or more selected from the group consisting of 1,3-diiodo-4-nitrobenzene and 1-iodo-4-nitrobenzene, but it is not limited thereto. When the catalyst is used, it may be used in an amount of 0.0001 to 0.1 mol, 0.0002 to 0.05 mol, or 0.0005 to 0.01 mol relative to 1 mol of the first sulfur compound.

The melt polymerization can be carried out as long as the conditions are capable of initiating the polymerization of the composition comprising the diiodo aromatic compound and the first sulfur compound. For example, melt polymerization can be carried out at a temperature of about 180 to 400°C, 180 to 350°C, or 180 to 300°C, and can be carried out at a pressure of about 0.001 to 500 Torr, 0.001 to 450 Torr, or 0.001 to 400 Torr . More specifically, the melt polymerization can be carried out under conditions of high temperature and reduced pressure, in which case, the polymerization reaction can be carried out for about 0.1 to 30 hours while the temperature is increased and the pressure is decreased (from a temperature of about 180 to 250° C. and a temperature of about 50° C.). Initial reaction conditions to a pressure of 450 Torr up to final reaction conditions of a temperature of about 270 to 350°C and a pressure of about 0.001 to 20 Torr). More specifically, the melt polymerization can be carried out under final reaction conditions of a temperature of about 280 to 300°C and a pressure of about 0.1 to 2 Torr.

Meanwhile, although the mixing order of the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor is not particularly limited, the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor may be mixed at the same time, or the polymerization may be inhibited The agent is added to the mixture comprising the diiodo aromatic compound and the first sulfur compound, thereby preparing a composition for melt polymerization.

In the case where the polymerization inhibitor is not mixed with the diiodo aromatic compound and the first sulfur compound at the same time, the timing of adding the polymerization inhibitor is not particularly limited. It can be determined in consideration of the final molecular weight of the target polyarylene sulfide. For example, it can be added when about 0 to 30%, 30 to 70%, or 70 to 100% by weight of the diiodoaromatic compound used in the initial reaction has been consumed by the reaction. Alternatively, the polymerization inhibitor can be added when the molecular weight of the polymerization product reaches a certain level. For example, when the molecular weight of the polymerization reaction product reaches 10% or more, 20% or more, 30% or more, 40% or more, 50% or more of the final molecular weight of the target polyarylene sulfide, 60% or higher, 70% or higher, 80% or higher, or 90% or higher, or 90% or lower, 80% or lower, 70% or lower, 60% or lower, At 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less, a polymerization inhibitor can be added. The molecular weight of the polymerization product can be determined, for example, by gel permeation chromatography.

In addition, before adding the polymerization inhibitor, the composition containing the diiodo aromatic compound and the first sulfur compound may be melt-mixed. In this case, the catalyst may also be added to the composition in the melt-mixing step. Melt-mixing is not particularly limited as long as the composition can be completely melt-mixed. For example, it can be carried out at a temperature of, for example, about 130 to 200°C or about 160 to 190°C. If such melt mixing is carried out, subsequent melt polymerization can be carried out more easily. The first polyarylene sulfide resin post-treated with a compatibilizer

The post-treated first polyarylene sulfide resin can be prepared by post-treating the first polyarylene sulfide resin with a compatibilizer.

Additionally, the post-treated first polyarylene sulfide resin may include the first polyarylene sulfide resin and end groups derived from a compatibilizer.

The first polyarylene sulfide resin is as described above.

The compatibilizer used for post-treatment of the first polyarylene sulfide resin may be a compound containing at least one functional group selected from the group consisting of: carboxyl group, carboxylate group, hydroxyl group, amine group, amide group, Silyl group, thioether group and sulfonate group. Specifically, the compatibilizer may be one or more compounds represented by one of Formulas 4 to 6 below. [Formula 4]

Y ¹ and Y ² are each independently selected from the group consisting of hydrogen, halo, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ , wherein B ¹ to B ⁷ are each independently selected from the group consisting of hydrogen radicals, sodium cations, lithium cations, substituted or unsubstituted alkyl groups having 1 to 3 carbon atoms, and substituted or unsubstituted Phenyl, Z ^1' to Z ^4' are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups having 1 or 2 carbon atoms, and those having 1 or 2 carbon atoms substituted or unsubstituted alkenyl, and p ¹ and p ² are each independently an integer from 1 to 3, with the proviso that at least one of Y ¹ and Y ² is selected from the group consisting of: -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ .

When Z ^1' and Z ^2' are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring. When Z ^3' and Z ^4' are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring.

When p ¹ or p ² is 2 or more, two or more Y ¹ or Y ² bonded to one aromatic ring may be the same or different from each other. In addition, Z ^1' and Z ^3' may be the same or different from each other, and Z ^2' and Z ^4' may be the same or different from each other.

A substituted alkyl group having 1 or 2 carbon atoms or a substituted alkenyl group having 1 or 2 carbon atoms among Z ^1' to Z ^4' may each independently have an alkane having 1 or 2 carbon atoms group or phenyl substituent.

In addition, the substituted alkyl group and the substituted phenyl group having 1 to 3 carbon atoms in B ¹ to B ⁷ may each independently have a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group.

Z ^1' and Z ^2' can be bonded to two adjacent carbon atoms, and Z ^3' and Z ^4' can be bonded to two adjacent carbon atoms. In addition, at least one or two or more of Z ^1' to Z ^4' may not be a hydrogen group. [Formula 5]

Y ³ to Y ⁶ are each independently selected from the group consisting of hydrogen, halo, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ , wherein B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R ^1' to R ^4' are each independently a group having 1 to 3 carbon atoms. An alkylene group of 5 carbon atoms, with the limitation that at least one of Y ³ and Y ⁶ is selected from the group consisting of: -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ . Here, at least one of Y ³ to Y ⁶ may be -SB ⁹ , wherein B ⁹ is a hydrogen group. [Formula 6]

Y ⁷ to Y ¹² are each independently selected from the group consisting of hydrogen, halo, OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ , wherein B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, and R ^5' and R ^6' are each independently a group having 1 to 5 An alkyl group with a carbon atom.

In addition, specifically, the compatibilizer may be at least one selected from the group consisting of: 2,2'-dithiobisdibenzoic acid, 4,4'-aminophenyl disulfide, bis(3 -hydroxyphenyl) disulfide and bis(4-hydroxyphenyl) disulfide, but they are not particularly limited thereto.

The compatibilizer may cause a substitution reaction of the iodine atom that may be located at the terminal of the first polyarylene sulfide resin, or it may not cause a reaction under the action of the compatibilizer. If the first polyarylene sulfide resin is post-treated with a compatibilizer, the atmosphere of the main chain and/or the end of the first polyarylene sulfide resin can be changed from hydrophobicity to hydrophilicity. Therefore, the compatibility with other resins having hydrophilic functional groups and/or reactive groups, inorganic fillers, and the like can be enhanced. As a result, it is possible to enhance the mechanical strength of the final product using it, and to significantly reduce the amount of outgassing due to heating.

The compatibilizer can react with the first polyarylene sulfide resin to impart end groups to the first polyarylene sulfide resin. Therefore, the post-treated first polyarylene sulfide resin may have end groups derived from the compatibilizer.

A terminal group derived from a compatibilizer may refer to a functional group possessed by the compatibilizer. Specifically, since the compatibilizer can be a compound containing functional groups such as carboxyl group, carboxylate group, hydroxyl group, amine group, amide group, silyl group, thioether group and sulfonate group, etc. The end groups of the compatibilizer can also be functional groups such as carboxyl groups, carboxylate groups, hydroxyl groups, amine groups, amide groups, silyl groups, thioether groups and sulfonate groups.

[式8]

[式9]

More specifically, the end group derived from the compatibilizer may have a structure represented by one of Formulas 7 to 9 below. [Formula 7]

[Formula 8]

[Formula 9]

In the above formula, Z ^1' , Z ^2' , Y ¹ , Y ³ to Y ⁵ , Y ⁷ to Y ⁹ , R ^1' to R ^5' and p ¹ are as described above.

The compatibilizer may be used in an amount of 0.001 to 10% by weight, 0.001 to 5% by weight, 0.01 to 3% by weight, or 0.1 to 2% by weight, based on the total weight of the first polyarylene sulfide resin. If the first polyarylene sulfide resin is post-treated with a compatibilizer after its polymerization, the reaction efficiency of the compatibilizer is remarkably excellent compared to the case where the same compound is added as a polymerization inhibitor during the polymerization of the resin, so that the The functional group content retained in the final resin is maximized. In addition, the target content of functional groups introduced into the final resin via the compatibilizer can be achieved while reducing the amount of compatibilizer used. If the same compound is added as a polymerization inhibitor, the reaction efficiency is low because it may be decomposed or discharged during the reaction due to the high temperature environment necessary for the polymerization reaction. In addition, when the compatibilizer is added during the polymerization of the first polyarylene sulfide resin, the possible formation of by-products of the compatibilizer can be minimized. Therefore, if the first polyarylene sulfide resin is post-treated with a compatibilizer, it is possible to reduce the amount of polymerization inhibitor/compatibilizer that may cause outgassing and minimize by-products, thereby reducing the outgassing amount and at the same time Enhanced compatibility, resulting in improved physical properties such as tensile strength, tensile elongation and air tightness. In addition, since the outgassing of the first polyarylene sulfide resin post-treated with the compatibilizer as described above is reduced, the processability of the injection molding process can be improved, excellent cavity balance can be obtained, and the production cycle can be shortened. effect.

The post-treatment with the compatibilizer can be carried out by mixing at high temperature. High temperature mixing can be carried out at a temperature of 290 to 330°C. Additionally, it can be performed in a non-oxidative atmosphere to achieve a high degree of polymerization while preventing oxidative crosslinking reactions. In a non-oxidizing atmosphere, the gaseous oxygen concentration may be less than 5% by volume or less than 2% by volume. More specifically, it is substantially free of gaseous oxygen. If post-processing is performed through high temperature mixing, iodine that may be present at some ends of the first polyarylene sulfide resin is sufficiently removed, and the crystallinity becomes excellent, thereby reducing shrinkage. Thus, the dimensional stability of the final article made using the post-treated first polyarylene sulfide can be enhanced.

Alternatively, high temperature mixing can be carried out in a reactor capable of heating and stirring. For example, the reactor may be a reactor of various materials such as SUS. The high temperature mixing can be performed in a twin-screw extruder, and the length-to-diameter ratio (L/D) of the twin-screw extruder can be about 30 to 50. For example, the first polyarylene sulfide resin can be fed through the main feeder of a twin-screw extruder, and other polymeric materials, such as thermoplastic resins or thermoplastic elastomers, fillers, or the like, can be fed through a main feeder located in the extruder. The side feeders on the side of the exit machine are added separately. The position of the side feeder relative to the outlet can be about 1/3 to 1/2 of the entire barrel of the extruder, thereby preventing the filler from being damaged by the rotation and friction of the extrusion screw in the extruder. In addition, before feeding the first polyarylene sulfide resin to the main feeder, it may be mixed with other additives added in small amounts.

Meanwhile, the post-treated first polyarylene sulfide resin is mainly composed of arylene sulfide units, but it may generally contain in its main chain a disulfide bond represented by [-SS-] and is derived from the first polyarylene sulfide in the raw material. A unit of a sulfur compound. The final polyarylene sulfide resin formula containing units based on disulfide bonds may have the copolymer form proposed by Eastman (US Pat. No. 4,768,000). The structural formula of the copolymer can be represented by the following formula 1. [Formula 1] -(Ar-S) _x -(Ar-SS) _y -

In the post-treated first polyarylene sulfide resin, when the sum of x corresponding to the arylene sulfide structure and y corresponding to the copolymerized sulfide structure in Formula 1 is 1, the content of x may be 0.900 to 0.999 , 0.950 to 0.999 or 0.990 to 0.999. In addition, the disulfide bond fraction in the post-treated first polyarylene sulfide resin may be 0.001 to 10.0 wt %, specifically, 0.1 wt % or higher, 0.3 wt % or higher, 0.5 wt % or higher or 0.7 wt% or higher, and it may be 10.0 wt% or lower, 5.0 wt% or lower, 2.0 wt% or lower, 1.8 wt% or lower, 1.6 wt% or lower, 1.5 wt% wt % or less, 1.4 wt % or less, 1.3 wt % or less, 1.2 wt % or less, 1.1 wt % or less, or 1 wt % or less. In this specification, the disulfide bond fraction (% by weight) can be defined as the difference between the theoretical sulfur content in the polyarylene sulfide and the sulfur content measured by elemental analysis relative to the theoretical sulfur in the polyarylene sulfide Content fraction. [Equation 1] Disulfide bond fraction (wt%) = {(total sulfur weight detected by elemental analysis) - (theoretical sulfur weight in polyarylene sulfide)} / (theoretical sulfur weight in polyarylene sulfide)

The post-treated first polyarylene sulfide resin may contain iodine derived from a diiodo aromatic compound. Based on the total weight of the post-treated first polyarylene sulfide resin, the iodine content may be 100 to 10,000 ppm, specifically, 250 ppm or more, 500 ppm or more, 750 ppm or more, or 900 ppm ppm or more, and it can be 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less , 2,500 ppm or less, 2,250 ppm or less, 2,200 ppm or less, 2,100 ppm or less, 2,000 ppm or less, 1,900 ppm or less, or 1,800 ppm or less, 1,700 or less, 1,600 ppm or less, or 1,500 ppm or less.

The post-treated first polyarylene sulfide resin can have 10 poise or more, 100 poise or more, 500 poise or more, 1,000 poise or more, 5,000 poise or more, 10,000 poise or more Large, 15,000 poise or more, 17,000 poise or more, 18,000 poise or more, 19,000 poise or more, 20,000 poise or more, 21,000 poise or more, 21,000 poise or more, 22,000 poise or more, or 23,000 poise or more, and 70,000 poise or less, 50,000 poise or less, 40,000 poise or less, 30,000 poise or less, 25,000 poise or less, 23,000 poise or less, or 20,000 poise or less melting viscosity. In this specification, melt viscosity may be defined as the angle of 1.84 rad/s when the viscosity is measured by the frequency sweep method at 300°C with a rotating disk viscometer in the angular frequency range of 0.6 to 500 rad/s Viscosity at frequency.

Additionally, the nonlinearity index can be 0.001 or more, 0.01 or more, 0.05 or more, 0.09 or more, or 0.10 or more, and it can be 0.50 or less, 0.40 or less, 0.30 or more Small, 0.20 or less, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less, 0.10 or less. When the nonlinear index is adjusted to the above range, the post-treated polyarylene sulfide resin can have enhanced processability and good cavity balance. The nonlinear index may be an index of molecular weight or molecular structure in terms of linear, branched or cross-linked chains of the object to be measured. Generally, when this value is close to 0, it indicates that the molecular structure of the resin is linear. As the value increases, it indicates that there are many branched or cross-linked structures. In this specification, when the viscosity change is measured by the frequency sweep method at 300°C with a rotating disk viscometer in the shear rate range of 0.03 to 25 s ⁻¹ , the nonlinear exponent can be defined by the following equation 2 . [Equation 2] Nonlinear exponent = 1 - (melt viscosity at 17.3 s ^-1 shear rate) / (melt viscosity at 3.22 s ^-1 shear rate)

A post-treated first polyarylene sulfide resin having a non-linear index within the specified range as described above can be obtained, for example, by using the polyarylene sulfide resin in the melt polymerization process of the mixture for melt polymerization The molecular weight is increased to a certain extent, and the mixture includes a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor.

The post-treated first polyarylene sulfide resin may have 0.10 or greater, 0.20 or greater, 0.30 or greater, 0.40 or greater, 0.50 or greater, 0.60 or greater, 0.61 or greater, 0.62 or greater greater, or 0.65 or greater, and 1.00 or less, 0.90 or less, 0.80 or less, or 0.70 or less branching ratio (α). In this specification, α is calculated according to the Mark-Howink equation of Equation 3 below. In general, the closer α is to 1, the more linear the polymer is. The closer α is to 0, the higher the degree of polymer branching. [Equation 3] [η] = KM ^α

In the above equation, η is the intrinsic viscosity, M is the weight average molecular weight, and K is a constant.

In addition, the melting point of the post-treated first polyarylene sulfide resin may be 250 to 300°C, 260 to 300°C, 265 to 300°C, or 270 to 290°C. In this specification, the melting point can be measured by increasing the temperature from 30°C to 320°C at a rate of 10°C/min in a differential scanning calorimeter (DSC, model Q20 from TA Instrument), and then increasing the temperature Cool to 30°C, then increase the temperature again from 30°C to 320°C at a rate of 10°C/min.

The crystallization temperature of the post-treated first polyarylene sulfide resin may be 150 to 300°C, 200 to 250°C, 210 to 240°C, 215 to 230°C, or 216 to 225°C. If the crystallization temperature is increased, not only the crystallization rate is increased, but also the degree of crystallinity is affected, whereby the mechanical properties of the final composition can be enhanced. In this specification, the crystallization temperature can be measured by increasing the temperature from 30°C to 320°C at a rate of 10°C/min in a differential scanning calorimeter (DSC, model Q20 from TA Instrument), and then changing the The temperature was cooled to 30°C and then again increased from 30°C to 320°C at a rate of 10°C/min.

The molecular weight of the post-treated first polyarylene sulfide resin can be measured as weight average molecular weight, number average molecular weight, peak molecular weight, and the like. The weight-average molecular weight of the post-treated first polyarylene sulfide resin is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of mechanical strength, it may be 25,000 g/mol or more large, or 30,000 g/mol or more, 40,000 g/mol or more, or 50,000 g/mol or more, and from a cavity balance point of view, it may be 100,000 g/mol or more Lesser, 80,000 g/mol or less, 65,000 g/mol or less, or 55,000 g/mol or less. In addition, in order to achieve excellent mechanical strength and good cavity balance, the weight average molecular weight of the post-treated first polyarylene sulfide resin can be adjusted to 25,000 to 60,000 g/mol, 30,000 to 55,000 g/mol , 30,000 to 80,000 g/mol, or 60,000 to 100,000 g/mol. Additionally, the number average molecular weight can be 1,000 grams/mol or greater, 5,000 grams/mol or greater, 7,500 grams/mol or greater, 9,000 grams/mol or greater, 10,000 grams/mol or greater Large, 11,000 g/mol or more, 12,000 g/mol or more, or 12,400 g/mol or more, and 30,000 g/mol or less, 25,000 g/mol or less, 20,000 g/mol or less, 15,000 g/mol or less, 13,500 g/mol or less, 13,000 g/mol or less, or 12,000 g/mol or less. The peak molecular weight can be 10,000 g/mol or greater, 15,000 g/mol or greater, 20,000 g/mol or greater, 25,000 g/mol or greater, 27,000 g/mol or greater, or 27,900 g/mol or more, and 140,000 g/mol or less, 100,000 g/mol or less, 75,000 g/mol or less, 50,000 g/mol or less, 45,000 g/mol or less ear or less, 43,000 g/mol or less, 35,000 g/mol or less, or 30,000 g/mol or less.

The outgassing amount of the post-treated first polyarylene sulfide resin may be 0.001 to 0.50 wt %, 0.001 to 0.20 wt %, or 0.01 to 0.10 wt %. In this specification, a gas chromatography (GC) mass spectrometer can be used to quantify the outgassing amount in weight percent when a predetermined amount of a sample of polyarylene sulfide resin or resin composition is heated at 330°C for 20 minutes The amount of gas produced.

The end of the post-treated first polyarylene sulfide resin may contain a carboxyl group, a carboxylate group, a hydroxyl group, an amine group, an amide group, a silyl group, a thioether group, a sulfonate group, or the like. Specifically, it may contain a functional group derived from a compound represented by one of the above formulae 4 to 6.

The first polyarylene sulfide resin post-treated with a compatibilizer has excellent compatibility with other resins and inorganic fillers with hydrophilic functional groups and/or reactive groups. Therefore, the outgassing amount can be lower than that of the polyarylene sulfide resin without post-treatment. Additionally, the amount of polymerization inhibitor/compatibilizer that can cause outgassing can be reduced and by-products minimized compared to polyarylene sulfide resins prepared using the same compound as a polymerization inhibitor during resin polymerization. Thus, the outgassing amount can be reduced.

Also, while not being bound by any particular theory, since outgassing is reduced as described above, the addition of compatibilizers to polyarylene sulfide resins with post-treatment can improve the processability of the injection molding process, resulting in excellent cavity balance And produce the effect of shortening the production cycle.

In addition, because the compatibility of the first polyarylene sulfide resin post-treated with the compatibilizer is improved, it may be excellent in mechanical strength such as tensile strength and tensile elongation and air tightness. additive

The additive is not limited as long as it does not impair the effect of the present invention. Specifically, examples thereof include fiber reinforcements, inorganic fillers, antioxidants, stabilizers, processing heat stabilizers, plasticizers, mold release agents, colorants, lubricants, weatherability stabilizers, foaming agents, rust inhibitors agents, waxes, nucleating agents, other resin components, anti-drip agents, and another compatibilizer.

Examples of fiber-reinforced materials may include inorganic fiber materials such as 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, metal fiber materials such as stainless steel, aluminum, titanium, copper, and pearls; and organic fiber materials such as aramid fibers. Examples of inorganic fillers may include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbestos, aluminum silicate, zeolite, and pyrophyllite; Carbonates, such as calcium carbonate, magnesium carbonate, and dolomite; sulfates, such as calcium sulfate and barium sulfate; metal oxides, such as aluminum oxide, magnesium oxide, silicon dioxide, zirconium oxide, titanium dioxide, and iron oxide; glass Beads; glass flakes; ceramic beads; boron nitride; silicon carbide; and calcium phosphate. These fiber reinforcements and inorganic fillers may be used alone or in combination of two or more.

Specifically, glass fibers can be surface-treated to improve interfacial adhesion with resins, and epoxy resins and silanes with amine groups can be used for surface treatment. For example, the glass fibers may be aluminoborosilicate glass. In addition, the glass filler can have, for example, an average diameter of 6 to 15 μm and an average length of 2 to 8 mm or 2 to 6 mm.

Thermal stabilizers can be used to prevent the resin from decomposing due to heat and light during the resin preparation process or during its use. When the polyarylene sulfide resin is mixed or molded with other additives or resins, it can minimize side reactions that may occur in a high temperature environment, thereby enhancing the physical properties of the final polyarylene sulfide resin composition. Examples of heat stabilizers include metal heat stabilizers such as calcium magnesium zinc based heat stabilizers, calcium zinc based heat stabilizers, organotin based heat stabilizers, metal soap based heat stabilizers, barium zinc based heat stabilizers Stabilizers, epoxy zinc based thermal stabilizers, magnesium aluminum carbonate based thermal stabilizers, zinc based thermal stabilizers, lead based thermal stabilizers and non-metallic thermal stabilizers such as epoxy based thermal stabilizers And heat stabilizers based on organic phosphites. A commercially available heat stabilizer is Dubon's CLC-120, which is a magnesium aluminum carbonate based heat stabilizer.

In addition, primary phenolic stabilizers, secondary phosphorus stabilizers, and primary-secondary mixed type stabilizers can be used as thermal stabilizers. Preferably, both the primary and secondary stabilizers have high molecular weights or have excellent thermal stability when stored at elevated temperatures. In this regard, preferred stabilizers include ADEKA's AO-60 and AO-80, Chemtura's Ultanox 627A and Doverphos S9228 and the like.

In addition, the release agent may specifically be a silicone-based release agent, a wax-based release agent, a fluorine-based release agent, a surfactant-based release agent, or a mixed release agent. A commercially available release agent is Hi-Wax ^™ from Mitsui.

Nucleating agents can be used to speed up crystallization. The use of nucleating agents increases crystallinity, even in low temperature molds, thereby enhancing the surface characteristics of the resin. Nucleating agents can be inorganic materials that are thermally stable at high temperatures. Examples thereof may include talc, calcium silicate, silicon dioxide, boron nitride, and the like. In particular, boron nitride may be in the form of a hexagonal crystal system. As the purity, boron nitride having a B ₂ O ₃ content of 0.5 wt % or less based on the total weight of boron nitride can be used. Alternatively, boron nitride with a purity of 95% by weight or higher may be used.

In addition, other resins may be used in appropriate amounts according to the desired characteristics of the first polyarylene sulfide resin. Examples of such resins may include homopolymers or copolymers of monomers such as: ethylene, butene, pentene, butadiene, isoprene, chloroprene, styrene, alpha-methylbenzene Ethylene, vinyl acetate, vinyl chloride, acrylates, methacrylates and (meth)acrylonitrile; and homopolymers, random copolymers, block copolymers and graft copolymers of the following: polyesters, such as Polyurethane, polybutylene terephthalate and polyethylene terephthalate; polyacetal; polycarbonate; Polyetherketone; polyetheretherketone; polyimide; polyimide; polyetherimide; silicone resin; epoxy resin; phenoxy resin; liquid crystal polymer; and polyarylene ether.

Specifically, other resin components may contain elastomers to enhance impact strength. The elastomer may be selected from the group consisting of: polyvinyl chloride based elastomers, polyolefin based elastomers, polyurethane based elastomers, polyester based elastomers, polyamide based elastomers , Polybutadiene-based elastomers, and terpolymers of glycidyl methacrylate and methacrylate.

Additionally, other resin components may include thermoplastic elastomers (TPE). In particular, the thermoplastic elastomer may be thermoplastic polyether block amide (TPA), thermoplastic polyurethane elastomer (TPU), thermoplastic copolyester elastomer (TPC), based on styrene block copolymers thermoplastic elastomers (TPS), thermoplastic elastomers (TPV) made from thermoplastics and vulcanized elastomers, or the like. The thermoplastic elastomer may be an epoxy elastomer containing epoxy functional groups. For example, it can be a copolymer of ethylene and glycidyl methacrylate. A commercially available thermoplastic elastomer is IGETABOND ^® BF-E from Sumitomo.

The anti-drip agent can be used to prevent dripping when the polyarylene sulfide resin composition is burned. Anti-drip agents may include fluorine-based anti-drip agents. Specifically, the anti-drip agent may include fluorine-based resins (polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, and the like), perfluoroalkanesulfonic acid alkali metal salt compounds (perfluoromethanesulfonic acid) Sodium salt, potassium perfluoro-n-butane sulfonate, potassium perfluoro-tertiary butane sulfonate, sodium perfluorooctane sulfonate, calcium perfluoro-2-ethylhexane sulfonate and its analogs), Alkaline earth metal salt of fluorocarbon sulfonic acid. More specifically, it may include polytetrafluoroethylene. Commercially available anti-drip agents are Hannanotech's FS-100, FS-200 and FS-300.

Another compatibilizer refers to a compatibilizer added to the polyarylene sulfide resin composition in addition to the compatibilizer used for post-treatment of the first polyarylene sulfide resin. Specifically, another compatibilizer may be a compatibilizer other than the compound represented by one of the above formulae 4 to 6. For example, another compatibilizer may be an epoxysilane-based compatibilizer. Another commercially available compatibilizer is Silques ^t® A-186 and A-187 from Momentive Performance Materials.

In addition, the metal additive, especially when used together with the thermoplastic elastomer, can accelerate the compatibilization reaction between the polyarylene sulfide resin and the thermoplastic elastomer. Zinc salts, magnesium salts, calcium salts, sodium salts, lithium salts or the like can be used as metal additives. Preferred are metal additives that have thermal stability and can facilitate the reaction between the glycidyl functional group of the elastomer and the compatible functional group of the polyarylene sulfide resin. Preferred metal additives to meet these needs include zinc stearate (Sigma Aldrich-307564), calcium stearate (Sigma Aldrich-26411), magnesium acetate (Sigma Aldrich-228648), magnesium stearate (Sigma Aldrich-228648) Sigma Aldrich-415057), sodium stearate (Sigma Aldrich-S3381), lithium carbonate (Sigma Aldrich-203629) and the like.

The additive may specifically include at least one selected from the group consisting of fiber reinforcements, thermal stabilizers, and elastomers. Specifically, the additives may include thermal stabilizers. More specifically, the additives may include glass fibers or may include elastomers and thermal stabilizers. Post-treated first polyarylene sulfide resin composition

The resin composition for the gasket may include the post-treated first polyarylene sulfide resin and additives.

Specifically, the post-treated first polyarylene sulfide resin composition may contain 0.1 wt % or more, 1 wt % or more based on the total weight of the post-treated first polyarylene sulfide resin composition Large, 2 wt% or greater, 5 wt% or greater, 10 wt% or greater, 15 wt% or greater, 20 wt% or greater, 30 wt% or greater, 40 wt% or greater , 50 wt% or more, or 60 wt% or more, and 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less, 90 wt% or less Small, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less of the post-treated first polyarylene sulfide resin.

Meanwhile, based on the total weight of the post-treated first polyarylene sulfide resin composition, the post-treated first polyarylene sulfide resin composition may contain 0.01 wt % or more, 0.1 wt % or more, 1 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more or 30 wt% or more, and 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, or Additives in an amount of 15% by weight or less.

More specifically, based on the total weight of the post-treated first polyarylene sulfide resin composition, the post-treated first polyarylene sulfide resin composition may include 10 to 70 wt %, 10 to 60 wt % , 10 to 50% by weight, 15 to 45% by weight, 20 to 40% by weight, or 25 to 35% by weight of glass fibers, and 0.1 to 20% by weight, 1 to 20% by weight, 5 to 15% by weight, or elastomer in an amount of 7 to 10% by weight. Additionally, it may include a thermal stabilizer in an amount of 0.01 to 5 wt %, 0.01 to 2 wt %, or 0.05 to 1 wt % on the same basis.

In addition, based on the total weight of the post-treated first polyarylene sulfide resin composition, the post-treated first polyarylene sulfide resin composition may include glass fibers in an amount of 10 to 70 wt %, or 0.1 wt % respectively. Elastomers and thermal stabilizers in amounts of to 20% by weight and 0.01 to 5% by weight.

Compared with the first polyarylene sulfide resin composition not post-treated with a compatibilizer, the post-treated first polyarylene sulfide resin composition has good outgassing and produces excellent air tightness and cavity balance and mechanical strength. [ Hybrid polyarylene sulfide resin composition ]

According to one embodiment, there is provided a resin composition for a gasket (hereinafter referred to as a hybrid polyarylene sulfide resin composition) comprising: melting a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor A polymerized first polyarylene sulfide resin; a second polyarylene sulfide resin solution-polymerized from a dihalogen aromatic compound and a second sulfur compound; and an additive.

According to another embodiment, there is provided a method for preparing a gasket resin composition, comprising: preparing a first polyarylene sulfide resin melt-polymerized from a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; preparing a second polyarylene sulfide resin that is solution-polymerized from a dihalogen aromatic compound and a second sulfur compound; and mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin with additives.

The first polyarylene sulfide resin and additives are as described above. The second polyarylene sulfide resin

The second polyarylene sulfide resin can be prepared by solution polymerization of a dihalogen aromatic compound and a second sulfur compound.

The second polyarylene sulfide resin is not particularly limited as long as it is prepared by solution polymerization of a dihalogen aromatic compound and a second sulfur compound. The Macallum process is known as a commercial process for the preparation of such polyarylene sulfide resins in which p-dichlorobenzene and sodium sulfide are brought into solution in the presence of a polar organic solvent such as N-methylpyrrolidone polymerization. A typical method is disclosed in US Patent No. 2,513,188.

Solution polymerization can be carried out in the presence of an organic polar solvent. The organic polar solvent may be, for example, at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam, N-propylcaprolactamide, N-methylcaprolactamide, N-cyclohexyl Caprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone , N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-Cyclohexyl-2-pyrrolidone, N-methyl-2-piperidinone, N-methyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo - Hexamethyleneimine, hexamethylphosphoric acid triamide, hexaethyl triamide phosphate, tetramethyl urea, 1,3-dimethylethylidene urea, 1,3-dimethylethylidene urea, 1,3-dimethylpropylidene urea, 1-methyl-1-oxycyclobutane, 1-ethyl-1-oxycyclobutane, 1-phenyl-1- Pendant oxycyclobutane, 1-methyl-1-side oxyphosphine, 1-propyl-1-side oxyphosphine and 1-phenyl-1-side oxyphosphine. The organic polar solvent can be, for example, N-methylpyrrolidone.

Dihalogen aromatic compounds refer to compounds having an aromatic ring and two halogen groups directly bonded thereto. Here, the halogen atoms of the halogen group may each be an atom of fluorine, chlorine, bromine and iodine, and the two halogen groups present in the dihalogen aromatic compound may be the same or different from each other. More specifically, both halogen atoms can be chlorine. The dihalogen aromatic compound can be, for example, at least one selected from the group consisting of ortho-dihalobenzene, meta-dihalobenzene, para-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, Dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenylene, dihalodiphenylene and dihalobenzophenone. The dihalogen aromatic compound may be, for example, 1,4-dichlorobenzene, but it is not particularly limited thereto.

The second sulfur compound may be at least one selected from the group consisting of alkali metal sulfides and alkali metal sulfide-forming compounds capable of forming alkali metal sulfides. Additionally, the second sulfur compound may be at least one selected from the group consisting of an alkali metal hydrosulfide and a compound for forming an alkali metal hydrosulfide. The second sulfur compound can be, for example, an alkali metal hydrosulfide such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide, and an alkali metal sulfide such as lithium sulfide, sodium sulfide, potassium sulfide, Rubidium sulfide and cesium sulfide, but they are not particularly limited thereto. The alkali metal sulfide-forming compound or alkali metal sulfide-forming compound may be, for example, hydrogen sulfide. An alkali metal hydrosulfide (eg, NaSH) or an alkali metal sulfide (eg, Na2S) can be prepared by blowing _hydrogen sulfide into an alkali metal hydroxide (eg, NaOH). The second sulfur compound may be at least one selected from the group consisting of acid anhydrides, hydrates, and aqueous solutions. The second sulfur compound may be, for example, sodium sulfide hydrate, but it is not particularly limited thereto. Hybrid polyarylene sulfide resin composition

The resin composition for the gasket may contain the first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives.

Solution-polymerized polyarylene sulfide resins prepared by solution polymerization of dihalogen aromatic compounds and sulfur compounds have excellent physical properties, such as high crystallization temperature and high mechanical strength, but have the disadvantage of outgassing due to use Therefore, outgassing is high, resulting in low cavity balance. On the other hand, the melt-polymerized polyarylene sulfide resin prepared by melt-polymerizing a mixture comprising a diiodo aromatic compound, a sulfur compound and a polymerization inhibitor has significantly lower outgassing due to the characteristics of the preparation process, while Its disadvantage is its low mechanical strength, since it contains disulfide bonds as weak structures.

However, the present inventors have surprisingly found that a hybrid polyarylene sulfide resin composition can be prepared by mixing a solution-polymerized polyarylene sulfide resin with a melt-polymerized polyarylene sulfide resin, wherein the hybrid resin has the same properties as the molten polyarylene sulfide resin. The outgassing amount is as low as that of the polymerized polyarylene sulfide resin, and the mechanical strength and air tightness are equivalent to or better than that of the solution polymerized polyarylene sulfide resin with excellent cavity balance.

Although not limited to a specific theory, the effect of the hybrid resin composition can be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin is mixed with the second polyarylene sulfide resin, the disulfide bond of the first polyarylene sulfide resin can be cleaved to further react with the terminal halogen of the second polyarylene sulfide resin . Therefore, since the disulfide bond, which is the weak structure of the first polyarylene sulfide, is removed and the molecular weight is increased, and the halogen of the second polyarylene sulfide can be additionally removed, the mechanical properties can be enhanced, and the release can be significantly reduced. air volume.

The mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin and the additive may be performed through melt mixing. The melt mixing can be performed under any conditions as long as the conditions can melt the first polyarylene sulfide resin and the second polyarylene sulfide resin. For example, melt mixing can be carried out in a single-screw or twin-screw compounding extruder, polymerization reactor, kneader reactor, or the like. More specifically, melt mixing can be carried out in a twin-screw extruder, and can be carried out at a temperature of 280 to 330°C, preferably 290 to 310°C. In such a case, the discharge rate of the resin component may be 5 to 50 kg/hr at a rotation speed of 250 rpm, and may be adjusted to 20 to 35 kg/hr in consideration of dispersibility. Specifically, the ratio of the discharge rate (kg/hr) of the resin component to the rotational speed (rpm) of the screw (discharge rate/screw rotational speed) is preferably 0.08 to 0.14 kg/hr·rpm. Hybrid polyarylene sulfide resins with further reduced outgassing can be prepared by degassing in a reactor equipped with a vacuum line during mixing.

Based on the total weight of the hybrid polyarylene sulfide resin composition, the hybrid polyarylene sulfide resin composition may contain 0.1 wt % or more, 1 wt % or more, 2 wt % or more, 5 wt % or greater, 10 wt% or greater, 15 wt% or greater, 20 wt% or greater, 30 wt% or greater, 40 wt% or greater, 45 wt% or greater, 50 wt% or greater, 60 wt% or greater, or 70 wt% or greater, and 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less, 90 wt% or less, 89 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, 65 wt% or less, 60 wt% or The first polyarylene sulfide resin in an amount of lesser, 55 wt % or less, or 50 wt % or less.

In addition, based on the total weight of the hybrid polyarylene sulfide resin composition, the hybrid polyarylene sulfide resin composition may contain the second polyarylene sulfide resin in the following amounts: 0.1 wt % or more, 1 wt % or greater, 2 wt% or greater, 5 wt% or greater, 10 wt% or greater, 15 wt% or greater, 20 wt% or greater, and 99.9 wt% or less, 99 wt% or less, 90 wt% or less, 70 wt% or less, 50 wt% or less, 42 wt% or less, 40 wt% or less, 38 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, less than 20 wt%, 15 wt% or less, or 10 wt% or less.

In addition, the hybrid polyarylene sulfide resin composition may contain 10 to 99.9 wt %, more specifically, 20 to 99 wt %, 30 to 99 wt %, based on the total weight of the hybrid polyarylene sulfide resin composition , the first polyarylene sulfide resin and the second polyarylene sulfide resin in an amount of 30 to 95% by weight, 30 to 70% by weight, or 50 to 70% by weight.

Based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, the hybrid polyarylene sulfide resin composition may contain 30% by weight or less, specifically, 0.0001 to 30% by weight, more Specifically, 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, or 25 wt% or more, and 25 wt% or less, 20 wt% % or less, 15 wt% or less, 10 wt% or less, or 5 wt% or less of the second polyarylene sulfide resin. If the second polyarylene sulfide resin is used within the above range, the effect of mixing the first polyarylene sulfide resin with the second polyarylene sulfide resin becomes remarkable, whereby the outgassing amount is reduced, and the cavity balance can be enhanced and tensile elongation.

In addition, based on the total weight of the mixed polyarylene sulfide resin composition, the mixed polyarylene sulfide resin composition may contain 0.01 wt % or more, 0.1 wt % or more, 1 wt % or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, or 30 wt% or more, and 90 wt% or less, 80 wt% or less, 70 wt% or less , 60 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, or 15 wt% or less amount of additives.

More specifically, based on the total weight of the mixed polyarylene sulfide resin composition, the mixed polyarylene sulfide resin composition may contain 10 to 70% by weight, 10 to 60% by weight, 10 to 50% by weight, 15 to 45% by weight, 20 to 40% by weight, or 25 to 35% by weight glass fibers, and 0.1 to 20% by weight, 1 to 20% by weight, 5 to 15% by weight, or 7 to 10% by weight amount of elastomer. Additionally, it may include a thermal stabilizer in an amount of 0.01 to 5 wt %, 0.01 to 2 wt %, or 0.05 to 1 wt % on the same basis.

In addition, based on the total weight of the hybrid polyarylene sulfide resin composition, the hybrid polyarylene sulfide resin composition may contain glass fibers in an amount of 10 to 70 wt %, or 0.1 to 20 wt % and 0.01 to 0.01 wt %, respectively. Elastomer and thermal stabilizer in an amount of 5% by weight.

Meanwhile, the hybrid polyarylene sulfide resin refers to the resin composed of the first polyarylene sulfide and the second polyarylene sulfide, and the melt viscosity, nonlinear index, branching ratio (α) of the hybrid polyarylene sulfide resin , molecular weight and melting point are as described above for the post-treated first polyarylene sulfide resin.

In addition, the disulfide bond fraction in the hybrid polyarylene sulfide resin may be 0.001 to 10.0 wt %, specifically, 0.1 wt % or more, 0.3 wt % or more, 0.5 wt % or more, 0.75 wt % or more % by weight or more, or 1.0% by weight or more, and it can be 10.0% by weight or less, 5.0% by weight or less, 2.0% by weight or less, 1.8% by weight or less, 1.6% by weight, or less, or 1.4 wt% or less.

The hybrid polyarylene sulfide resin may contain iodine derived from a diiodo aromatic compound. Based on the total weight of the mixed polyarylene sulfide resin, the iodine content may be 1 to 10,000 ppm, specifically, 5 ppm or more, 10 ppm or more, 20 ppm or more, 40 ppm or more, 100 ppm or more, 500 ppm or more, or 1,000 ppm or more, and it can be 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, less than 2,300 ppm, 2,000 ppm or less, 1,900 ppm or less, or 1,800 ppm or less.

The crystallization temperature of the hybrid polyarylene sulfide resin may be as high as the crystallization temperature of the second polyarylene sulfide resin. For example, the hybrid polyarylene sulfide resin may have a crystallinity of 150 to 300°C, 200 to 280°C, 210 to 260°C, 210 to 270°C, 220 to 260°C, 225 to 255°C, or 230 to 250°C temperature. As the crystallization temperature of the hybrid polyarylene sulfide resin increases, not only does the crystallization rate increase, but also the degree of crystallinity is affected, thereby enhancing the mechanical properties of the final composition comprising the resin.

The hybrid polyarylene sulfide resin may have an outgassing amount of 0.001 to 5 wt %, specifically, 0.001 wt % or more, 0.01 wt % or more, 0.1 wt % or more, 0.2 wt % or more, 0.3 wt% or more, or 0.35 wt% or more, and 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.35 wt% or less , 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, 0.8 wt% or less, 0.6 wt% or less, or 0.5 wt% or less .

The hybrid polyarylene sulfide resin composition has the same low outgassing as the first polyarylene sulfide resin composition, has excellent cavity balance, and has an equivalent or better performance than the second polyarylene sulfide resin. Tensile strength, tensile elongation and air tightness. [ Post-treated mixed polyarylene sulfide resin composition ]

According to one embodiment, there is provided a resin composition for a gasket, comprising: a post-treated first polyarylene sulfide resin, wherein end groups derived from a compatibilizer are introduced into In the first polyarylene sulfide resin melt-polymerized with a monosulfur compound and a polymerization inhibitor; the second polyarylene sulfide resin by solution polymerization of a dihalogen aromatic compound and a second sulfur compound; and an additive.

According to another embodiment, there is provided a method for preparing a gasket resin composition, comprising: preparing a first polyarylene sulfide resin melt-polymerized from a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; preparing a second polyarylene sulfide resin that is solution-polymerized from a dihalogen aromatic compound and a second sulfur compound; mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin with additives; and using a compatibilizer for the second polyarylene sulfide resin A polyarylene sulfide resin is post-treated.

The post-treated first polyarylene sulfide resin, second polyarylene sulfide resin and additives are as described above. Post-treated mixed polyarylene sulfide resin composition

The resin composition for the gasket (hereinafter referred to as the post-treated hybrid polyarylene sulfide resin composition) may include the post-treated first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives . Its mixing is as described above.

However, the post-treatment of the first polyarylene sulfide resin may be performed before the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, may be performed simultaneously with the mixing, or may be performed after the mixing. Additionally, it may be performed before mixing and may be further performed simultaneously with or after mixing, and other combinations may exist without limitation. For example, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are fed to the twin-screw extruder and melt-mixed therein, the compatibilizer may be added to the twin-screw extruder by adding a compatibilizer to the twin-screw extruder. During the process, the first polyarylene sulfide resin is post-treated. In such a case, the conditions in the twin-screw extruder may be set so that the ratio of the discharge rate (kg/hr) of the resin component to the screw rotation speed (rpm) (discharge rate/screw rotation speed) is 0.02 to 0.2 kg /hr·rpm.

The end of the post-treated mixed-type polyarylene sulfide resin may contain functional groups such as carboxyl groups, carboxylate groups, hydroxyl groups, amine groups, amide groups, silane groups, thioether groups, and sulfonate groups.

Based on the total weight of the mixed polyarylene sulfide resin composition, the post-treated mixed polyarylene sulfide resin composition may contain 0.1 wt % or more, 1 wt % or more, 2 wt % or more , 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, and 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less , 90 wt% or less, 89 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, 65 wt% or less, The post-treated first polyarylene sulfide resin in an amount of 60 wt% or less, 55 wt% or less, or 50 wt% or less.

In addition, based on the total weight of the post-treated mixed-type polyarylene sulfide resin composition, the post-treated mixed-type polyarylene sulfide resin composition may contain 0.1 wt % or more, 1 wt % or more, 2 wt% or more, 5 wt% or more, 10 wt% or more, 15 wt% or more, or 20 wt% or more, and 99.9 wt% or less, 99 wt% or less , 90 wt% or less, 70 wt% or less, 50 wt% or less, 42 wt% or less, 40 wt% or less, 38 wt% or less, 30 wt% or less, The second polyarylene sulfide resin in an amount of 25 wt% or less, 20 wt% or less, less than 20 wt%, 15 wt% or less, or 10 wt% or less.

In addition, based on the total weight of the post-treated mixed-type polyarylene sulfide resin composition, the post-treated mixed-type polyarylene sulfide resin composition may contain 10 to 99.9 wt %, more specifically, 20 to 99 wt % % by weight, 30 to 99% by weight, 30 to 95% by weight, 30 to 70% by weight, or 50 to 70% by weight of the post-treated first polyarylene sulfide resin and the second polyarylene sulfide resin.

Based on the total weight of the post-treated first polyarylene sulfide resin and the second polyarylene sulfide resin, the post-treated hybrid polyarylene sulfide resin composition may contain 30% by weight or less, specifically , 0.0001 to 30% by weight, more specifically, 5% by weight or greater, 10% by weight or greater, 15% by weight or greater, 20% by weight or greater, or 25% by weight or greater, and 25 The second polyarylene sulfide resin in an amount of wt % or less, 20 wt % or less, 15 wt % or less, 10 wt % or less, or 5 wt % or less. If the second polyarylene sulfide resin is used within the above range, the effect of mixing the post-treated first polyarylene sulfide resin with the second polyarylene sulfide resin becomes significant, thereby reducing the outgassing amount, and Can enhance cavity balance, tensile strength and tensile elongation.

In addition, based on the total weight of the post-treated mixed-type polyarylene sulfide resin composition, the post-treated mixed-type polyarylene sulfide resin composition may contain 0.01% by weight or more, 0.1% by weight or more, 1 wt% or greater, 5 wt% or greater, 10 wt% or greater, 20 wt% or greater, or 30 wt% or greater, and 90 wt% or less, 80 wt% or less , 70 wt% or less, 60 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, or additives in an amount of 15% by weight or less.

More specifically, based on the total weight of the post-treated mixed-type polyarylene sulfide resin composition, the post-treated mixed-type polyarylene sulfide resin composition may contain 10 to 70 wt %, 10 to 60 wt % , 10 to 50% by weight, 15 to 45% by weight, 20 to 40% by weight, or 25 to 35% by weight of glass fibers, and 0.1 to 20% by weight, 1 to 20% by weight, 5 to 15% by weight, or elastomer in an amount of 7 to 10% by weight. Additionally, it may include a thermal stabilizer in an amount of 0.01 to 5 wt %, 0.01 to 2 wt %, or 0.05 to 1 wt % on the same basis.

In addition, the post-treated hybrid polyarylene sulfide resin composition may contain glass fibers in an amount of 10 to 70 wt %, or 0.1 wt %, respectively, based on the total weight of the post-treated hybrid polyarylene sulfide resin composition. Elastomers and thermal stabilizers in amounts of to 20% by weight and 0.01 to 5% by weight.

Meanwhile, the post-treated mixed-type polyarylene sulfide resin refers to the resin composed of the post-treated first polyarylene sulfide and the second polyarylene sulfide resin, and the post-treated mixed-type polyarylene sulfide resin has Melt viscosity, nonlinear index, branching ratio (α), molecular weight, melting point, disulfide bond fraction, iodine content, crystallization temperature, and outgassing amount are as described above for the hybrid polyarylene sulfide resin.

The post-treated mixed-type polyarylene sulfide resin composition has the same low outgassing as the first polyarylene sulfide resin composition, has excellent cavity balance, and is superior to the first polyarylene sulfide resin composition The mechanical strength and air tightness of the composite and the second polyarylene sulfide resin composition.

While not being bound by a particular theory, this effect is achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin is mixed with the second polyarylene sulfide resin, the disulfide bond of the first polyarylene sulfide resin can be cleaved to further react with the terminal halogen of the second polyarylene sulfide resin . Therefore, since the disulfide bond, which is the weak structure of the first polyarylene sulfide, is removed and the molecular weight is increased, and the halogen of the second polyarylene sulfide can be additionally removed, the mechanical properties can be enhanced, and the release can be significantly reduced. air volume.

In addition, since the first polyarylene sulfide resin is post-treated with a compatibilizer, the compatibility with other resins and inorganic fillers having hydrophilic functional groups and/or reactive groups is enhanced. Thus, the mechanical strength of the final product made by using the mixed resin can be enhanced, and the amount of outgassing due to heating can be significantly reduced. In addition, the reaction efficiency of the compatibilizer is remarkably excellent compared to the case where the same compound is added as a polymerization inhibitor during the polymerization of the resin, so that the content of functional groups remaining in the final resin can be maximized. In addition, the target content of functional groups introduced into the final resin via the compatibilizer can be achieved while reducing the amount of compatibilizer used. Therefore, if it is post-treated with a compatibilizer, the amount of polymerization inhibitor/compatibilizer that can cause outgassing can be reduced, and by-products that the compatibilizer may form in the high temperature environment required for polymerization can be reduced At a minimum, outgassing is thereby further reduced and compatibility is enhanced at the same time, resulting in excellent cavity balance and improved physical properties such as tensile strength, tensile elongation, and air tightness. [ gasket ]

According to one embodiment, there is provided a gasket including a resin composition for the gasket.

According to another embodiment, there is provided a secondary battery comprising: an outer body having an opening; a sealing body for sealing the opening of the outer body; an anode plate, a cathode plate, and an electrolyte disposed in the outer body; an anode disposed in the anode A separator between the plate and the cathode plate; an anode terminal electrically connected to the anode plate; a cathode terminal electrically connected to the cathode plate; and a secondary battery gasket in contact with either the anode terminal or the cathode terminal.

The resin composition for the gasket may comprise a first polyarylene sulfide resin, a post-treated first polyarylene sulfide resin, a second polyarylene sulfide resin, a hybrid polyarylene sulfide resin, or a post-treated polyarylene sulfide resin mixed polyarylene sulfide resins, as described above.

In addition, the gasket for a secondary battery may be a molded product obtained from the resin composition for the gasket. The resin composition for the gasket can be molded into various forms by various methods without limitation. Typically, the resin composition can be cut into pellets, and the pellets are supplied to a molding machine and melt-molded to finally obtain a molded article having a desired shape. Melt forming can be eg injection moulding, extrusion moulding, compression moulding or the like, especially injection moulding. The mold temperature for injection molding can be about 50°C or higher, 60°C or higher, or 80°C or higher from a crystallization standpoint, and can be about 190°C from a sample deformation standpoint or lower, 170°C or lower, or 160°C or lower. Shaped articles can be in various forms of films, sheets or fibers.

The resin composition for gaskets as described above has good air tightness and excellent cavity balance and mechanical strength. Therefore, since molding defects are reduced, it can maintain airtightness even when mechanical or thermal shock is applied, and productivity can be improved, whereby it can be advantageously used as a secondary battery gasket. Examples for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples only illustrate the present invention, and the scope of the present invention is not limited thereto. [ Preparation Example ] 1. Preparation Example a1 of the First Polyarylene Sulfide Resin : Preparation of PPS a1

A 5 liter reactor equipped with a thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of nitrogen purging and vacuum application was charged with 5,240 g of p-diiodobenzene and 450 g of elemental sulfur. The composition containing p-diiodobenzene and elemental sulfur in the reactor was heated to 180°C to fully melt and mix. Subsequently, the polymerization reaction was carried out while the temperature was increased and the pressure was decreased, gradually changing from the initial reaction conditions of 220°C and 350 Torr to the final reaction conditions of 300°C and 1 Torr or less. A sample of the polymerization product was taken, and the molecular weight of the sample was measured by gel permeation chromatography. When the weight average molecular weight (Mw) of the polymerization reaction product reached about 15,000 g/mol, 24 g of diphenyl disulfide (Sigma Aldrich-169021) was added as a polymerization inhibitor, and the reaction was carried out for 1 hour. Next, the pressure was gradually decreased to 0.5 Torr or less, and the reaction was further performed for 1 hour. Next, the reaction was terminated, and the resin thus prepared was processed into pellets using a small strand cutter to obtain PPS a1 as the first polyarylene sulfide resin. Preparation Example a2 : Preparation of PPS a2

About 1,500 g of PPS a2 was prepared as the first polyarylene sulfide resin in the same manner as in Preparation Example a1, except that 4.5 g of 2,2'-dithiodibenzoic acid (Sigma Aldrich-43761, 95.0% purity was used) or higher) instead of 24 g of diphenyl disulfide as a polymerization inhibitor. 2. Second polyarylene sulfide resin preparation example b : preparation of PPS b

The reactor was charged with 3,027 g of sodium sulfide pentahydrate and 5,400 g of NMP as a polar organic solvent, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the mixture of water and NMP. Next, a solution of 2,646 g of p-dichlorobenzene and 17.01 g of p-chlorobenzoic acid dissolved in 2,070 g of NMP was added to the reactor, and a polymerization reaction was performed at 220 to 240° C. in a nitrogen atmosphere for 8 to 12 hours . After the reactor was cooled, the polymerization product was collected and filtered. The filter cake was further washed with 2,880 g of NMP, 10 liters of ion-exchanged water was added to the filter cake containing NMP, and the mixture was stirred in an autoclave at 200° C. for 10 minutes, and further filtered. The last filtered cake was dried at 130°C for 3 hours to prepare PPS b as the second polyarylene sulfide resin. 3. Preparation Example c1 of the Post-treated First Polyarylene Sulfide Resin : Preparation of PPS c1

99.7 parts by weight (1,496 g) of the first polyarylene sulfide resin (PPS a1) prepared according to Preparation Example a1 and 0.3 parts by weight (4.5 g) of 2,2'-dithiodibenzoic acid (Sigma) as a compatibilizer were used. Aldrich-43761, 95.0% pure or higher) was fed into a twin screw compounding extruder and melt blended at a temperature of 300°C. The melt-blended polyarylene sulfide resin was processed into pellets using a small strand cutter to prepare PPS c1 as the post-treated first polyarylene sulfide resin. Preparation Example c2 : Preparation of PPS c2

PPS c2 was prepared as the post-treated first polyarylene sulfide resin in the same manner as in Preparation Example c1, except that 0.3 parts by weight of 4,4'-dithiodiphenylamine (Sigma Aldrich-369462, 98 purity) was used % or higher) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. Preparation Example c3 : Preparation of PPS c3

PPS c3 was prepared as the post-treated first polyarylene sulfide resin in the same manner as in Preparation Example c1, except that 0.3 parts by weight of bis(3-hydroxyphenyl) disulfide (TCI (Tokyo Chemical)- B3149, with a purity of 97.0% or higher (GC)) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. Preparation Example c4 : Preparation of PPS c4

PPS c4 was prepared as the post-treated first polyarylene sulfide resin in the same manner as in Preparation Example c1, except that 0.3 parts by weight of bis(4-hydroxyphenyl)disulfide (TCI (Tokyo Chemical)- B3827, with a purity of 98.0% or higher (GC)) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. Preparation Example c5 : Preparation of PPS c5

PPS c5 was prepared as the post-treated first polyarylene sulfide resin in the same manner as in Preparation Example c1, except that 0.3 parts by weight of 3-(triethoxysilyl)propan-1-thiol (SiSiB -PC2310, China Power Chemical) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. Preparation Example c6 : Preparation of PPS c6

PPS c6 was prepared as the post-treated first polyarylene sulfide resin in the same manner as in Preparation Example c1, except that 0.3 parts by weight of 1,2-bis(3-(triethoxysilyl)propyl) was used ) disulfane (SiSiB-PC2200, China Power Chemical) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. 4. Polyarylene sulfide resin composition

The first polyarylene sulfide resin, the second polyarylene sulfide resin, and the post-treated first polyarylene sulfide resin prepared according to the preparation examples were fed to the twin-screw compound in the weight ratios shown in the following Tables 1 to 5 Extruder (TEM-35B, Toshiba Kikai Corporation) and melt blending at 300°C. This was processed into pellets using a small wire cutter to prepare a polyarylene sulfide resin composition (the composition before the additives were mixed). Subsequently, the polyarylene sulfide resin composition was uniformly mixed with glass fibers, elastomers, and heat stabilizers in the weight ratios shown in the following Tables 1 to 4 using a rotating drum and passed through a twin-screw compounding extruder at 300° C. (TEM-35B, Toshiba Kikai Corporation) melt blending. This was processed into pellets using a small wire cutter to prepare a polyarylene sulfide resin composition (the composition after additive mixing).

Specifically, PPS A1-1 to PPS A2 were obtained as the first polyarylene sulfide resin composition, PPS B1 and PPS B2 were obtained as the second polyarylene sulfide resin composition, and PPS C1-1 to PPS C2 were obtained as the after-treatment The first polyarylene sulfide resin composition, PPS D1-1 to PPS D2-5 as mixed polyarylene sulfide resin composition, and PPS E1-1 to PPS E2-4 as post-treated mixed polyarylene Sulfide resin composition. [Table 1] PPS C1-1 PPS C1-2 PPS C1-3 PPS C1-4 PPS C1-5 PPS C1-6 PPS C1-7 PPS C1-8 PPS C1-9 PPS C2 PPS A1-1 PPS A1-2 PPS A2 P* PPS a1 - - - - - - - - - - 60.0 - 89.8 PPS a2 - - - - - - - - - - - 60.0 - PPS c1 60.0 - - - - - 59.8 57.0 56.8 89.8 - - - PPS c2 - 60.0 - - - - - - - - - - - PPS c3 - - 60.0 - - - - - - - - - - PPS c4 - - - 60.0 - - - - - - - - - PPS c5 - - - - 60.0 - - - - - - - - PPS c6 - - - - - 60.0 - - - - - - - A* glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 - 40.0 40.0 - Elastomer - - - - - - - 3.0 3.0 10.0 - - 10.0 Heat stabilizers - - - - - - 0.2 - 0.2 0.2 - - 0.2 total 100.0 *P: PPS, A: Additives [Table 2] PPS D1-1 PPS D1-2 PPS D1-3 PPS D1-4 PPS D1-5 PPS D1-6 PPS D1-7 PPS D1-8 PPS B1 PPS PPS a1 55.0 50.0 42.0 40.0 30.0 49.8 47.5 47.3 - PPS b 5.0 10.0 18.0 20.0 30.0 10.0 9.5 9.5 60.0 additive glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - - - 3.0 3.0 - Heat stabilizers - - - - - 0.2 - 0.2 - total 100.0 [table 3] PPS D2-1 PPS D2-2 PPS D2-3 PPS D2-4 PPS D2-5 PPS B2 PPS PPS a1 82.3 74.8 62.9 44.9 63.0 - PPS b 7.5 15.0 26.9 44.9 27.0 90.0 stabilizer Elastomer 10.0 10.0 10.0 10.0 10.0 10.0 Heat stabilizers 0.2 0.2 0.2 0.2 - - total 100.0 [Table 4] PPS E1-1 PPS E1-2 PPS E1-3 PPS E1-4 PPS E1-5 PPS E1-6 PPS E1-7 PPS E1-8 PPS E1-9 PPS E1-10 PPS E1-11 PPS E1-12 PPS E1-13 P* PPS b 5.0 10.0 18.0 20.0 30.0 10.0 9.5 9.5 9.5 9.5 9.5 9.5 9.5 PPS c1 55.0 50.0 42.0 40.0 30.0 49.8 47.5 47.3 - - - - - PPS c2 - - - - - - - 47.3 - - - - PPS c3 - - - - - - - - 47.3 - - - PPS c4 - - - - - - - - - 47.3 - - PPS c5 - - - - - - - - - - 47.3 - PPS c6 - - - - - - - - - - - 47.3 A* glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - - - 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Heat stabilizers - - - - - 0.2 - 0.2 0.2 0.2 0.2 0.2 0.2 total 100.0 *P: PPS, A: Additives [Table 5] PPS E2-1 PPS E2-2 PPS E2-3 PPS E2-4 PPS PPS b 7.5 15.0 26.9 44.9 PPS c1 82.3 74.8 62.9 44.9 additive Elastomer 10.0 10.0 10.0 10.0 Heat stabilizers 0.2 0.2 0.2 0.2 total 100.0

Glass fibers, elastomers, and thermal stabilizers are specifically shown in Table 6 below. [Table 6] component Material glass fiber Glass fiber FT-523 from Owen Corning, diameter 10 µm, length 4 mm, surface treated with epoxy silane Elastomer IGETABOND® BF-E, Sumitomo Heat stabilizers CLC-120 (hydrated magnesium aluminum hydroxide carbonate) [ Test example ]

According to the following method, for the polyarylene sulfide resin composition prepared according to the above preparation example, the melting point, crystallization temperature, melt viscosity, nonlinear index, molecular weight, branch ratio, dichondral Sulfur bond fraction, outgassing and iodine content, and measuring/deriving outgassing, cavity balance, tensile strength, tensile elongation and air tightness of these compositions after additive mixing. The results are shown in Tables 7 to 13 below. (1) Melting point (Tm) and crystallization temperature (Tc)

The temperature was increased from 30°C to 320°C at a rate of 10°C/min in a differential scanning calorimeter (DSC, model Q20 from TA Instrument) and then cooled to 30°C at a rate of 10°C/min , and then the temperature was again increased from 30°C to 320°C at a rate of 10°C/min to measure the melting point and crystallization temperature. (2) Melt viscosity (MV) and nonlinear index

Melt viscosity is defined as the viscosity at an angular frequency of 1.84 rad/s when the viscosity is measured by the frequency sweep method at 300°C with a rotating disk viscometer in the angular frequency range of 0.6 to 500 rad/s.

The nonlinear index is calculated by Equation 2 below. [Equation 2] Nonlinear exponent = 1 - (melt viscosity at 17.3 s ^-1 shear rate) / (melt viscosity at 3.22 s ^-1 shear rate) (3) number average molecular weight (Mn) , weight average molecular weight (Mw) and peak molecular weight (Mp)

The number average molecular weight, weight average molecular weight, and peak molecular weight of the polyarylene sulfide resin composition were each measured by gel permeation chromatography under the following measurement conditions. In all measures of molecular weight, six types of monodisperse polystyrene were used for calibration. [Measurement conditions for gel permeation chromatography] Instrument: Agilent PL-220 Column: Agilent, PLgel pore size 105Å + 104Å + 500Å + 50Å (4 columns) Column temperature: 210°C Solvent: 1-chloronaphthalene Measurement method: triple system detector (RI, viscometer, light diffuser 15° and 90°) (4) Branch ratio (α)

The branching ratio is defined as the value of alpha calculated by applying the viscosity measured by the triple system detector to the Mark-Howink equation of Equation 3 below. The Mark-Houwink equation is a relational expression between the molecular weight of the polymer and the intrinsic viscosity, and the branching ratio (α) represents the degree of branching of the polymer. That is, the closer the value is to 1, the more linear the polymer is. The closer the value is to 0, the higher the degree of polymer branching. [Equation 3] [η] = KХM ^α

In the above equation, η is the intrinsic viscosity, M is the weight average molecular weight, and K is a constant. (5) Disulfide bond (-SS-) fraction

The disulfide bond fraction is calculated according to Equation 1 below. [Equation 1] Disulfide bond fraction (wt%) = {(total sulfur weight detected by elemental analysis) - (theoretical sulfur weight in polyarylene sulfide)} / (theoretical sulfur in polyarylene sulfide Weight) (6) Outgassing

Composition before additive mixing: The amount of gas generated when a predetermined amount of a sample of the polyarylene sulfide resin composition was heated at 330° C. for 30 minutes was quantified (weight percent) using a gas chromatography (GC) mass spectrometer.

Composition after additive mixing: The amount of gas generated when a predetermined amount of a sample of the polyarylene sulfide resin composition was heated at 325°C for 15 minutes was quantified (weight percent) using a gas chromatography (GC) mass spectrometer. (7) Iodine content

The iodine content in the polyarylene sulfide resin composition was measured by ion chromatography (IC) using Thermo Scientific IC (AQF) and ICS-2500 (Mitsubishi AQF-100). (8) Cavity balance

Using a washer mold with 40 cavities, the polyarylene sulfide resin compositions were each injection molded under minimum molding conditions, wherein the cavity (C1) at the position closest to the main spool was completely filled. The molding conditions were set to a 75-ton molding machine, a barrel temperature of 320°C, a mold temperature of 140°C, and no holding pressure. Among the cavities in the same runner as the cavity (C1), the filling degree (% by weight) of the cavity (C10) farthest from the main bobbin is based on the molding product of the cavity (C10) and the molding of the cavity (C1) Product weight ratio calculation. The higher the filling degree of the cavity (C10), the better the cavity balance. Therefore, the cavity balance of each polyarylene sulfide resin composition was evaluated based on the filling degree based on the following criteria. AA: 90% by weight or more A: 80% by weight to less than 90% by weight B: 70% by weight to less than 80% by weight C: 60% by weight to less than 70% by weight D: less than 60% by weight (9) Tensile strength and tensile elongation

The tensile strength and tensile elongation of the polyarylene sulfide resin composition were measured using Zwick's Z010 according to the ISO 527-2 method. (10) Air tightness

The polyarylene sulfide resin composition was processed into a molded article having a box shape of 8 mm (length) x 8 mm (width) x 10 mm (thickness). The electrolyte was injected into the molded article and sealed under constant stress (at 10% strain) with the 8 mm (length) x 8 mm (width) x 3 mm (thickness) flat plate used in the compressive stress relaxation test to prepare the sample For air tightness testing. Here, the electrolyte is a solution in which LiPF ₆ is dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate (1:1 volume ratio) at a concentration of 1 mol/liter. The samples for the air tightness test were kept under dry heat at 60° C. for 100 hours, and the degree of leakage of the electrolyte was checked. Results were evaluated based on the following criteria. ○: No electrolyte leakage after 100 hours ×: Electrolyte leakage after 100 hours Post-treated first polyarylene sulfide resin composition [Table 7] Example Comparative example PPS C1-1 PPS C1-2 PPS C1-3 PPS C1-4 PPS C1-5 PPS C1-6 PPS C1-7 PPS C1-8 PPS C1-9 PPS A1-1 PPS A1-2 C* PPS a1 - - - - - - - - - 60.0 - PPS a2 - - - - - - - - - - 60.0 PPS c1 60.0 - - - - - 59.8 57.0 56.8 - - PPS c2 - 60.0 - - - - - - - - - PPS c3 - - 60.0 - - - - - - - - PPS c4 - - - 60.0 - - - - - - - PPS c5 - - - - 60.0 - - - - - - PPS c6 - - - - - 60.0 - - - - - glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - - - - 3.0 3.0 - - Heat stabilizers - - - - - - 0.2 - 0.2 - - total 100.0 BA* Disulfide bond fraction (wt%) 1.1 1.0 1.0 0.9 1.1 1.4 1.1 1.1 1.1 2.1 2.3 Outgassing (wt%) 0.05 0.05 0.05 0.05 0.09 0.02 0.05 0.05 0.05 0.21 0.30 Melt viscosity (poise) 2200 2300 2180 2140 1950 2290 2200 2200 2200 2100 2030 nonlinear index 0.10 0.10 0.11 0.12 0.10 0.09 0.10 0.10 0.10 0.15 0.13 Mn (g/mol) 12000 12000 12400 12700 12500 12800 12000 12000 12000 11000 11500 Mw (g/mol) 42400 44200 43200 43500 43100 43400 42400 42400 42400 42800 45600 Mp (g/mol) 28000 28000 27900 27700 27600 27600 28000 28000 28000 27800 28100 alpha 0.61 0.60 0.61 0.62 0.61 0.63 0.61 0.61 0.61 0.58 0.59 Iodine content (ppm) 1860 1800 1950 1910 2100 1780 1860 1860 1860 2300 12100 Melting point(℃) 280.3 280.4 280.0 280.1 280.8 281.8 280.3 280.3 280.3 280.5 280.7 Crystallization temperature (℃) 218.7 217.9 216.4 219.9 220.0 216.4 218.7 218.7 218.7 216.2 215.4 AA* Outgassing (wt%) 0.15 0.14 0.15 0.15 0.16 0.16 0.17 0.21 0.28 0.15 0.29 Cavity balance A AA A AA A A A AA AA B B Tensile strength (MPa) 190 194 185 192 196 201 193 185 186 175 178 Tensile elongation (%) 1.7 1.8 1.7 1.8 1.9 1.9 1.8 2.2 2.3 1.7 1.8 air tightness ○ ○ ○ ○ ○ ○ ○ ○ ○ × × *C: Components of the composition, BA: Before additives are mixed, AA: After additives are mixed

As can be seen from the above table, compared to PPS A1-1 comprising the first polyarylene sulfide resin and additives without compatibilizer post-treatment and the first polymer prepared by using the compound of formula 4 as the polymerization inhibitor PPS A1-2 of arylene sulfide resin and additives, PPS C1-1 to PPS C1-9 containing the first polyarylene sulfide resin and additives post-treated with a compatibilizer maintain a good outgassing amount, while it is in the mold cavity All aspects of balance, tensile strength, tensile elongation and air tightness are excellent. [Table 8] example Comparative example PPS C2 PPS A2 Components of the composition PPS a1 - 89.8 PPS c1 89.8 - Elastomer 10.0 10.0 Heat stabilizers 0.2 0.2 total 100.0 Before additives are mixed Disulfide bond fraction (wt%) 1.1 2.1 Outgassing (wt%) 0.05 0.21 Melt viscosity (poise) 2200 2100 nonlinear index 0.10 0.15 Mn (g/mol) 12000 11000 Mw (g/mol) 42400 42800 Mp (g/mol) 28000 27800 alpha 0.61 0.58 Iodine content (ppm) 1860 2300 Melting point(℃) 280.3 280.5 Crystallization temperature (℃) 218.7 216.2 After the additives are mixed Outgassing (wt%) 1.40 1.40 Cavity balance A B Tensile strength (MPa) 58.0 47.5 Tensile elongation (%) 5.0 2.5 air tightness ○ ×

As can be seen from the above table, the PPS containing the first polyarylene sulfide resin and additives post-treated with a compatibilizer is compared to PPS A2 containing the first polyarylene sulfide resin and additives that have not been post-treated with a compatibilizer C2 maintains good outgassing while it is excellent in all aspects of cavity balance, tensile strength, tensile elongation and air tightness. Hybrid polyarylene sulfide resin composition [Table 9] Example Comparative example PPS D1-1 PPS D1-2 PPS D1-3 PPS D1-6 PPS D1-7 PPS D1-8 PPS A1-1 PPS B1 PPS D1-4 PPS D1-5 C* PPS a1 55.0 50.0 42.0 49.8 47.5 47.3 60.0 - 40.0 30.0 PPS b 5.0 10.0 18.0 10.0 9.5 9.5 - 60.0 20.0 30.0 glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - 3.0 3.0 - - - - Heat stabilizers - - - 0.2 - 0.2 - - - - total 100.0 BA* Disulfide bond fraction (wt%) 1.8 1.6 1.2 1.6 1.6 1.6 2.1 ND 1.3 1.2 Outgassing (wt%) 0.33 0.47 0.56 0.47 0.47 0.47 0.21 1.42 1.12 1.31 Melt viscosity (poise) 2100 2360 2760 2360 2360 2360 2100 2010 2220 2300 nonlinear index 0.15 0.11 0.09 0.11 0.11 0.11 0.15 0.04 0.12 0.12 Mn (g/mol) 11100 12500 14300 12500 12500 12500 11000 11400 13100 13600 Mw (g/mol) 41200 48500 51200 48500 48500 48500 42800 43800 48600 49500 Mp (g/mol) 27900 32900 38000 32900 32900 32900 27800 38000 37200 37900 alpha 0.60 0.68 0.70 0.68 0.68 0.68 0.58 0.77 0.74 0.75 Iodine content (ppm) 2500 1860 1690 1860 1860 1860 2300 ND 1440 1230 Melting point(℃) 280.2 279.9 280.2 279.9 279.9 279.9 280.5 281.5 279.5 279.0 Crystallization temperature (℃) 237.6 239.1 239.4 239.1 239.1 239.1 216.2 238.7 237.5 238.0 AA* Outgassing (wt%) 0.211 0.203 0.186 0.196 0.293 0.305 0.250 0.563 0.521 0.541 Cavity balance A A A A A A B B B B Tensile strength (MPa) 191 198 205 196 179 176 175 185 185 179 Tensile elongation (%) 1.8 1.9 2.0 1.9 2.1 2.1 1.6 1.7 1.7 1.6 air tightness ○ ○ ○ ○ ○ ○ × ○ ○ ○ *C: Components of the composition, BA: Before additives are mixed, AA: After additives are mixed

As can be seen from the above table, compared to PPS A1-1 comprising the first polyarylene sulfide resin and the additive, the PPS D1-1 to PPS comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive D1-3 and PPS D1-6 to PPS D1-8 are excellent in cavity balance, tensile strength, tensile elongation and air tightness. Compared to PPS B1 comprising the second polyarylene sulfide resin and additives, it is excellent in outgassing amount, cavity balance and tensile elongation.

Although the tensile strengths of PPS D1-7 and PPS D1-8 further comprising an elastomer as an additive were slightly lower than those of PPS D1-1 to PPS D1-6, they still had higher tensile strengths and significantly higher tensile strengths than PPS A1-1. The tensile elongation is higher than that of PPS A1-1 and PPS B1.

In addition, compared to PPS D1-4 and PPS D1-5 having a second polyarylene sulfide resin content of more than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, PPS D1-1 to PPS D1-3 and PPS D1-6 to PPS D1-8 were clearly excellent in outgassing, cavity balance and tensile elongation. [Table 10] example Comparative example PPS D2-1 PPS D2-2 PPS D2-3 PPS D2-5 PPS A2-1 PPS B2 PPS D2-4 C* PPS a1 82.3 74.8 62.9 63.0 89.8 - 44.9 PPS b 7.5 15.0 26.9 27.0 - 90.0 44.9 Elastomer 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Heat stabilizers 0.2 0.2 0.2 - 0.2 - 0.2 total 100.0 BA* Disulfide bond fraction (wt%) 1.8 1.6 1.2 1.2 2.1 ND 1.2 Outgassing (wt%) 0.33 0.47 0.56 0.56 0.21 1.42 1.31 Melt viscosity (poise) 2100 2360 2760 2760 2100 2010 2300 nonlinear index 0.15 0.11 0.09 0.09 0.15 0.04 0.12 Mn (g/mol) 11100 12500 14300 14300 11000 11400 13600 Mw (g/mol) 41200 48500 51200 51200 42800 43800 49500 Mp (g/mol) 27900 32900 38000 38000 27800 38000 37900 alpha 0.60 0.68 0.70 0.70 0.58 0.77 0.75 Iodine content (ppm) 2500 1860 1690 1690 2300 ND 1230 Melting point(℃) 280.2 279.9 280.2 280.2 280.5 281.5 279.0 Crystallization temperature (℃) 237.6 239.1 239.4 239.4 216.2 238.7 238.0 AA* Outgassing (wt%) 1.32 1.29 1.49 1.35 1.40 2.53 1.88 Cavity balance A A A A B B B Tensile strength (MPa) 56.0 57.0 58.0 52.0 47.5 51.5 57.3 Tensile elongation (%) 5.0 4.6 4.9 4.3 2.5 3.4 3.7 air tightness ○ ○ ○ ○ × ○ ○ *C: Components of the composition, BA: Before additives are mixed, AA: After additives are mixed

As can be seen from the above table, compared to PPS A2-1 comprising the first polyarylene sulfide resin and the additive, the PPS D2-1 to PPS comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive D2-3 and PPS D2-5 are excellent in cavity balance, tensile strength, tensile elongation and air tightness. Compared to PPS B2 containing the second polyarylene sulfide resin and additives, it is excellent in outgassing, cavity balance and tensile elongation.

In addition, compared to PPS D2-4 having a second polyarylene sulfide resin content of more than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, PPS D2-1 to PPS D2-3 and PPS D2-5 are clearly excellent in outgassing, cavity balance and tensile elongation.

In detail, PPS D2-1 to PPS D2-3 further including a heat stabilizer as an additive were significantly excellent in tensile strength and tensile elongation compared to PPS D2-5 not including a heat stabilizer. Post-treated mixed polyarylene sulfide resin composition [Table 11] example PPS E1-1 PPS E1-2 PPS E1-3 PPS E1-6 PPS E1-7 PPS E1-8 PPS E1-9 PPS E1-10 PPS E1-11 PPS E1-12 PPS E1-13 C* PPS a - - - - - - - - - - - PPS b 5.0 10.0 18.0 10.0 9.5 9.5 9.5 9.5 9.5 9.5 9.5 PPS c1 55.0 50.0 42.0 49.8 47.5 47.3 - - - - - PPS c2 - - - - - - 47.3 - - - - PPS c3 - - - - - - - 47.3 - - - PPS c4 - - - - - - - - 47.3 - - PPS c5 - - - - - - - - - 47.3 - PPS c6 - - - - - - - - - - 47.3 glass fiber 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Heat stabilizers - - - 0.2 - 0.2 0.2 0.2 0.2 0.2 0.2 total 100.0 BA* Disulfide bond fraction (wt%) 1.6 1.4 1.0 1.4 1.4 1.4 1.3 1.4 1.3 1.3 1.5 Outgassing (wt%) 0.13 0.27 0.35 0.27 0.27 0.27 0.31 0.30 0.29 0.29 0.31 Melt viscosity (poise) 2200 2430 2640 2430 2430 2430 2350 2210 2290 2100 2250 nonlinear index 0.15 0.11 0.10 0.11 0.11 0.11 0.12 0.12 0.11 0.10 0.11 Mn (g/mol) 12200 12800 15000 12800 12800 12800 12500 12100 12300 12800 13400 Mw (g/mol) 43000 48800 51500 48800 48800 48800 48100 47800 48200 48100 49800 Mp (g/mol) 28100 33700 38600 33700 33700 33700 32500 31200 33600 32500 34800 alpha 0.62 0.68 0.71 0.68 0.68 0.68 0.70 0.69 0.71 0.69 0.70 Iodine content (ppm) 2300 1440 1450 1440 1440 1440 1420 1460 1350 1560 1250 Melting point(℃) 280.0 280.4 280.9 280.4 280.4 280.4 280.1 279.6 280.6 280.8 279.7 Crystallization temperature (℃) 237.5 236.4 238.4 236.4 236.4 236.4 236.9 237.1 237.2 236.8 237.5 AA* Outgassing (wt%) 0.295 0.315 0.325 0.299 0.282 0.289 0.300 0.272 0.265 0.312 0.320 Cavity balance AA AA AA AA AA AA AA AA AA AA AA Tensile strength (MPa) 198 202 210 206 185 183 184 180 183 183 187 Tensile elongation (%) 1.9 2.0 2.1 2.0 2.4 2.5 2.5 2.5 2.3 2.4 2.6 air tightness ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ *C: Components of the composition, BA: Before additive mixing, AA: After additive mixing [Table 12] Comparative example PPS A1-1 PPS B1 PPS D1-2 PPS E1-4 PPS E1-5 Components of the composition PPS a1 60.0 - 50.0 - - PPS b - 60.0 10.0 20.0 30.0 PPS c1 - - 40.0 40.0 30.0 PPS c2 - - - - - PPS c3 - - - - - PPS c4 - - - - - PPS c5 - - - - - PPS c6 - - - - - glass fiber 40.0 40.0 40.0 40.0 40.0 Elastomer - - - - - Heat stabilizers - - - - - total 100.0 Before additives are mixed Disulfide bond fraction (wt%) 2.1 ND 1.6 1.2 1.0 Outgassing (wt%) 0.21 1.42 0.47 0.77 0.91 Melt viscosity (poise) 2100 2010 2360 2030 1930 nonlinear index 0.15 0.04 0.11 0.10 0.11 Mn (g/mol) 11000 11400 12500 11800 10900 Mw (g/mol) 42800 43800 48500 47800 43500 Mp (g/mol) 27800 38000 32900 30700 31200 alpha 0.58 0.77 0.68 0.69 0.70 Iodine content (ppm) 2300 ND 1860 1240 1010 Melting point(℃) 280.5 281.5 279.9 280.4 279.8 Crystallization temperature (℃) 216.2 238.7 239.1 236.4 238.5 After the additives are mixed Outgassing (wt%) 0.250 0.563 0.203 0.386 0.470 Cavity balance B B A A A Tensile strength (MPa) 175 185 198 185 180 Tensile elongation (%) 1.6 1.7 1.9 1.8 1.7 air tightness × ○ ○ ○ ○

As can be seen from the above table, compared to PPS A1-1 comprising the first polyarylene sulfide resin and the additive, the PPS E1 comprising the post-treated first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive -1 to PPS E1-3 and PPS E1-6 to PPS E1-13 are excellent in cavity balance, tensile strength, tensile elongation and air tightness. Compared to PPS B1 comprising the second polyarylene sulfide resin and additives, it is excellent in outgassing amount, cavity balance and tensile elongation. Compared to PPS D1-2 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and additives, it is excellent in cavity balance and tensile elongation.

Although the tensile strengths of PPS E1-7 and PPS E1-13 further comprising an elastomer as an additive were slightly lower than those of PPS E1-1 to PPS E1-6, they still had higher tensile strengths and significantly higher tensile strengths than PPS A1-1. Higher tensile elongation than PPS A1-1, PPS B1 and PPS D1-2.

In addition, compared to PPS E1-4 and PPS E1-5 having a second polyarylene sulfide resin content of more than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, PPS E1-1 to PPS E1-3 and PPS E1-6 to PPS E1-13 were excellent in outgassing, cavity balance and tensile elongation. [Table 13] Example Comparative example PPS E2-1 PPS E2-2 PPS E2-3 PPS A2 PPS B2 PPS D2-2 PPS E2-4 Components of the composition PPS a - - - 89.8 - 74.8 - PPS b 7.5 15.0 26.9 - 90.0 15.0 44.9 PPS c1 82.3 74.8 62.9 - - - 44.9 Elastomer 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Heat stabilizers 0.2 0.2 0.2 0.2 - 0.2 0.2 total 100.0 Before additives are mixed Disulfide bond fraction (wt%) 1.6 1.4 1.0 2.1 ND 1.6 1.0 Outgassing (wt%) 0.13 0.27 0.35 0.21 1.42 0.47 0.91 Melt viscosity (poise) 2200 2430 2640 2100 2010 2360 1930 nonlinear index 0.15 0.11 0.10 0.15 0.04 0.11 0.11 Mn (g/mol) 12200 12800 15000 11000 11400 12500 10900 Mw (g/mol) 43000 48800 51500 42800 43800 48500 43500 Mp (g/mol) 28100 33700 38600 27800 38000 32900 31200 alpha 0.62 0.68 0.71 0.58 0.77 0.68 0.70 Iodine content (ppm) 2300 1440 1450 2300 ND 1860 1010 Melting point(℃) 280.0 280.4 280.9 280.5 281.5 279.9 279.8 Crystallization temperature (℃) 237.5 236.4 238.4 216.2 238.7 239.1 238.5 After the additives are mixed Outgassing (wt%) 1.41 1.49 1.60 1.40 2.53 1.29 2.22 Cavity balance AA AA AA B B A A Tensile strength (MPa) 63 65 67 47.5 51.5 57 55.0 Tensile elongation (%) 6.5 7.5 8.6 2.5 3.4 4.6 5.0 air tightness ○ ○ ○ × ○ ○ ○

As can be seen from the table above, the PPS E2-1 comprising the post-treated first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive is compared to the PPS A2 comprising the first polyarylene sulfide resin and the additive To PPS E2-3 is excellent in cavity balance, tensile strength, tensile elongation and air tightness. Compared to PPS B2 comprising the second polyarylene sulfide resin and additives, it is excellent in outgassing, cavity balance, tensile strength and tensile elongation. Compared with PPS D2-2 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and additives, it is excellent in cavity balance and tensile elongation.

In addition, compared to PPS E2-4 having a second polyarylene sulfide resin content of more than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, PPS E2-1 to PPS E2-3 is excellent in outgassing, cavity balance, tensile strength and tensile elongation.

Claims (17)

A resin composition for a gasket, comprising: a post-treated first polyarylene sulfide resin, wherein an end group derived from a compatibilizer is introduced into a diiodo aromatic compound, a first sulfur compound and a first polyarylene sulfide resin melt-polymerized with a polymerization inhibitor; and At least one additive selected from the group consisting of a glass fiber, an elastomer, and a thermal stabilizer. The resin composition for a gasket according to claim 1, wherein the additive comprises the glass fiber or comprises the elastomer and the thermal stabilizer. The resin composition for a gasket according to claim 1, wherein the outgassing amount of the post-treated first polyarylene sulfide resin is 0.001 to 0.20% by weight, or The disulfide bond fraction in the post-treated first polyarylene sulfide resin is 0.1 to 2.0 wt %. The resin composition for a gasket according to claim 1, wherein the compatibilizer comprises at least one functional group selected from the group consisting of: a carboxyl group, a carboxylate group, a hydroxyl group, an amine group, a amide group, monosilyl group, monosulfide group and monosulfonate group. The resin composition for a gasket according to claim 1, wherein the compatibilizer is a compound represented by one of the following formulas 4 to 6: [Formula 4]

In the above formula, Y ¹ and Y ² are each independently selected from the group consisting of monohydrogen, monohalo, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ , wherein B ¹ to B ⁷ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted one having 1 to 3 carbon atoms Alkyl, and a substituted or unsubstituted phenyl, Z ^1' to Z ^4' are each independently selected from the group consisting of a hydrogen, a substituted or unsubstituted having 1 or 2 carbon atoms the alkyl group, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms, and p ¹ and p ² are each independently an integer from 1 to 3, wherein when Z ^1' and Z ^2' When it is an alkenyl group with 2 carbon atoms and is bonded to two adjacent carbon atoms, it can be connected to each other to form a benzene ring, when Z ^3' and Z ^4' are an alkenyl group with 2 carbon atoms And when bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring, the substituted alkyl group having 1 or 2 carbon atoms in Z ^1' to Z ^4' or the substituted alkyl group having 1 or 2 carbon atoms. The substituted alkenyl groups of 1 carbon atoms each independently have a substituent containing either an alkyl group or a phenyl group of 1 or 2 carbon atoms, and the substituted alkenyl groups of B ¹ to B ⁷ having 1 to 3 carbon atoms The substituted alkyl group or the substituted phenyl group each independently has a substituent containing an alkyl group or a phenyl group of 1 or 2 carbon atoms, with the limitation that at least one of Y ¹ and Y ² is selected Free from the group consisting of -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ ; [Formula 5]

In the above formula, Y ³ to Y ⁶ are each independently selected from the group consisting of monohydrogen, monohalo, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ , wherein B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R ^1' to R ^4' are each independently selected from the group consisting of an alkylene group and an alkoxy group each having 1 to 5 carbon atoms, with the proviso that at least one of Y ³ and Y ⁶ is -SB ⁹ , where B ⁹ is hydrogen, [Formula 6]

In the above formula, Y ⁷ to Y ¹² are each independently selected from the group consisting of monohydrogen, monohalo, OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ , wherein B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, and R ^5′ and R ^6' is each independently an alkylene group having 1 to 5 carbon atoms. The resin composition for a gasket according to claim 1, wherein the first polyarylene sulfide resin is post-treated using the compatibilizer at a temperature of 280 to 330°C. A resin composition for a gasket, comprising: a first polyarylene sulfide resin melt-polymerized from a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor; a second polyarylene sulfide resin polymerized from a solution of a dihalogen aromatic compound and a second sulfur compound; and at least one additive selected from the group consisting of a glass fiber, an elastomer, and a thermal stabilizer, Wherein, based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, the second polyarylene sulfide resin is used in an amount of 0.0001 to 30% by weight. The resin composition for a gasket according to claim 7, wherein the mixed-type polyarylene sulfide resin composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin has 0.01 to 1.40% by weight of Outgassing amount and disulfide bond fraction of 0.1 to 2.0 wt%. The resin composition for a gasket according to claim 7, wherein the first polyarylene sulfide resin and the second polyarylene sulfide resin are melt-mixed at 280 to 330°C. The resin composition for a gasket of claim 7, based on the total weight of the resin composition, comprising the first polyarylene sulfide resin in an amount of 1 to 89 wt %, the first polyarylene sulfide resin in an amount of 1 to 38 wt % amount of the second polyarylene sulfide resin, and the glass fiber in an amount of 10 to 70% by weight. The resin composition for a gasket of claim 7, based on the total weight of the resin composition, comprising the first polyarylene sulfide resin in an amount of 1 to 98 wt %, the first polyarylene sulfide resin in an amount of 1 to 42 wt % amount of the second polyarylene sulfide resin, the elastomer in an amount of 0.1 to 20 wt %, and the thermal stabilizer in an amount of 0.01 to 5 wt %. A resin composition for a gasket, comprising: a post-treated first polyarylene sulfide resin, wherein an end group derived from a compatibilizer is introduced into a diiodo aromatic compound, a first sulfur compound and a first polyarylene sulfide resin melt-polymerized with a polymerization inhibitor; a second polyarylene sulfide resin polymerized from a solution of a dihalogen aromatic compound and a second sulfur compound; and at least one additive selected from the group consisting of a glass fiber, an elastomer, and a thermal stabilizer, Wherein, based on the total weight of the post-treated first polyarylene sulfide resin and the second polyarylene sulfide resin, the second polyarylene sulfide resin is used in an amount of 0.0001 to 30% by weight. The resin composition for a gasket according to claim 12, wherein the post-treated mixed polyarylene sulfide composed of the post-treated first polyarylene sulfide resin and the second polyarylene sulfide resin The ether resin has an outgassing amount of 0.01 to 1.40 wt % and a disulfide bond fraction of 0.1 to 2.0 wt %. The resin composition for a gasket of claim 12, based on the total weight of the resin composition, comprising the post-treated first polyarylene sulfide resin, 1 to 89 wt % in an amount of 1 to 89 wt % The second polyarylene sulfide resin in an amount of 38% by weight, and the glass fiber in an amount of 10 to 70% by weight. The resin composition for a gasket of claim 12, based on the total weight of the resin composition, comprising the post-treated first polyarylene sulfide resin, 1 to 98 wt % in an amount of 1 to 98 wt % The second polyarylene sulfide resin in an amount of 42% by weight, the elastomer in an amount of 0.1 to 20% by weight, and the thermal stabilizer in an amount of 0.01 to 5% by weight. A gasket for a secondary battery comprising a molded article obtained from the resin composition for a gasket as in any one of Claims 1 to 15. A secondary battery comprising: an outer body having an opening; a sealing body for sealing the opening of the outer body; an anode plate, a cathode plate and an electrolyte disposed in the outer body; a separator arranged between the anode plate and the cathode plate; an anode terminal electrically connected to the anode plate; a cathode terminal electrically connected to the cathode plate; and A gasket for a secondary battery as claimed in claim 16 in contact with the anode terminal or the cathode terminal.