KR20210152726A - Resin composition for gasket and gasket for secondary battery comprising the same - Google Patents

Abstract

An embodiment relates to a novel polyarylene sulfide resin composition for a gasket and a gasket for a secondary battery including the same. The resin composition for a gasket of the embodiment can have a low outgas amount, excellent airtightness, cavity balance, tensile strength, tensile elongation, and/or crystallinity.

Description

A resin composition for a gasket and a gasket for a secondary battery comprising the same

The embodiment relates to a resin composition for a gasket and a gasket for a secondary battery comprising the same.

As a driving power source for portable devices, 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 is accommodated in a battery case (external body) having an opening provided with an electrolyte for immersing the electrode plate group and the electrode plate group including a positive electrode plate, a negative electrode plate, and a separator disposed therebetween, and the battery case sealed by a sealing body for sealing the opening of the In such a sealed secondary battery, for example, a gasket is provided at a contact point between a positive electrode plate or a negative electrode plate electrically connected to the positive electrode or negative electrode terminal to prevent a short circuit between a pair of terminals or to prevent leakage of electrolyte.

Regarding the material of such a gasket, the technique using polyarylene sulfide resin is reported (refer patent document 1). Polyphenylene sulfide is the only polyarylene sulfide currently being mass-marketed, and its production method includes a solution polymerization method that polymerizes paradichlorobenzene and sodium sulfide as raw materials in N-methylpyrrolidone solvent (patented Reference 2), there is a melt polymerization method in which a diiodine aromatic compound and a sulfur compound are polymerized at a high temperature as raw materials without using a solvent.

Polyphenylene sulfide resin prepared by solution polymerization is known to adversely affect the heat resistance, flame resistance and durability of molded products because of the use of solvent and the amount of outgas due to chlorine contained in the raw material.

The polyphenylene sulfide resin prepared by the melt polymerization method does not use a solvent, so it has excellent productivity and cost structure, has a low amount of outgas, and has improved effects such as excellent corrosion resistance because it does not use a chlorine-based raw material. However, due to the non-polar end group of the resin, it is difficult to modify it to have desired properties due to its low reactivity with processing additives, which limits its use and usage, and the disulfide bond derived from the sulfur compound used as a raw material has a weak structure in the resin. There is a limitation in that the mechanical strength is not sufficient because it acts as a

Japanese Patent Laid-Open Publication No. 8-321287 US Patent No. 2,513,188

Such a gasket for a secondary battery is basically required to have chemical resistance to the electrolyte and excellent airtightness. In addition, the gasket needs to have excellent mechanical strength so that it can maintain airtightness even in an environment where the internal pressure rises as a mechanical shock is applied to the secondary battery or the solvent is vaporized or decomposed inside the secondary battery by heating to generate gas. do.

On the other hand, molded products such as gaskets can be manufactured by injection molding a resin using a mold having a plurality of cavities in order to simultaneously manufacture a plurality of molded products. Since productivity is lowered when molding defects are not generated, the resin used for gaskets and the like is required to have a good cavity balance.

As a result of intensive research to solve these problems, the present inventors found that, when polyarylene sulfide resin post-processed with a compatibilizer is used for the manufacture of gaskets, the cavity balance can be improved while achieving both excellent airtightness and mechanical strength. did In addition, by mixing a solution-polymerized polyarylene sulfide resin and a melt-polymerized polyarylene sulfide resin, it was found that a gasket having excellent airtightness and mechanical strength while maintaining a good cavity balance could be manufactured, thereby completing the present invention. .

Accordingly, in the embodiments to be described later, it is an object to provide a novel polyarylene sulfide resin composition for a gasket and a gasket for a secondary battery including the same.

According to one embodiment, the diiodo aromatic compound, the first sulfur compound and the polymerization inhibitor are melt-polymerized in the first polyarylene sulfide resin, a post-processed first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced; and an additive, a resin composition for a gasket is provided.

According to another exemplary embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and an additive, a resin composition for a gasket is provided.

According to another embodiment, a post-processed first polyarylene sulfide in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized Suzy; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and an additive, a resin composition for a gasket is provided.

According to another embodiment, there is provided a gasket for a secondary battery, which includes a molded article in which the above-described resin composition for a gasket is molded.

According to another embodiment, the exterior body having an opening; a sealing body sealing the opening of the exterior body; a positive electrode plate, a negative electrode plate, and an electrolyte provided inside the exterior body; a separator provided between the positive electrode plate and the negative electrode plate; a positive electrode terminal electrically connected to the positive electrode plate; a negative terminal electrically connected to the negative electrode plate; A secondary battery is provided, including the above-described gasket for secondary battery in contact with the positive terminal or the negative terminal.

The polyarylene sulfide resin composition for a gasket of the embodiment may have a low outgas amount, excellent airtightness, cavity balance, tensile strength, tensile elongation, and/or crystallinity.

Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

[Post-processed polyarylene sulfide resin composition]

According to an embodiment, the first polyarylene sulfide resin is post-processed in which terminal groups derived from a compatibilizer are introduced into the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized; and an additive, a resin composition for a gasket (hereinafter, post-processed first polyarylene sulfide resin composition) is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; mixing an additive and the first polyarylene sulfide resin; and post-processing the first polyarylene sulfide resin using a compatibilizer.

First polyarylene sulfide resin

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

The diiodo aromatic compound refers to a compound having an aromatic ring and two iodine atoms directly bonded thereto. Diiodo aromatic compounds include diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododiphenyl. It may be at least one selected from the group consisting of sulfones, but is not limited thereto.

The aromatic ring of the diiodo aromatic compound is a halo group excluding an iodo group, a phenyl group, a hydroxy group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone and an aryl ketone from the group consisting of It may be substituted by at least one selected substituent. When the aromatic ring of the diiodo aromatic compound is substituted with the above substituent, the diiodo aromatic compound having an aromatic ring substituted with the above substituent is a diiodo having an unsubstituted aromatic ring from the viewpoint of crystallinity and heat resistance of the resin. It may also be 0.0001 to 5% by weight or 0.001 to 1% by weight based on the aromatic compound. The substitution positions of the two iodo groups in the diiodo aromatic compound are not particularly limited, but the two substitution positions may be far from each other in the molecule, and may be the para position or the 4,4'-position.

The diiodo aromatic compound is present in an amount of 0.5 to 2.0 moles, 0.55 to 1.9 moles, 0.6 to 1.8 moles, 0.65 to 1.7 moles, 0.7 to 1.6 moles, 0.75 to 1.5 moles, or 0.8 to 1.4 moles based on 1 mole of the first sulfur compound. can be included as The diiodo aromatic compound may be, for example, p-diiodobenzene.

The first sulfur compound may be a single sulfur. Single sulfur refers to a compound composed of sulfur atoms. The single 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 S 8} and S ₆ that is generally available, but limited thereto doesn't happen The purity, form, and particle size of the single sulfur are not particularly limited. For example, the form of single sulfur may be in the form of granules or powders that are solid at room temperature (23° C.). In addition, the particle diameter of the single sulfur may be 0.001 to 10 mm, 0.01 to 5 mm, or 0.01 to 3 mm, but is not particularly limited thereto.

The polymerization inhibitor may 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 is a compound capable of introducing at least one functional group selected from the group consisting of -OR, -SR, -COOR, -NHR, -SO _{3 R, -NHCOR, etc. at the end of the main chain of the polyarylene sulfide resin} may be, wherein R may 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 include the functional group, and the functional group may be generated by a polymerization stop reaction or the like. In addition, the polymerization inhibitor may be a compound not containing the functional group, specifically, diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole , N-cyclohexyl-2-benzothiazolylsulfenamide, 2-(morpholinothio)benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide It may be at least one compound.

In addition, the polymerization inhibitor may be one or more of the compounds represented by the following Chemical Formulas 1 to 3, specifically, may be a compound represented by the Chemical Formula 1.

[Formula 1]

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

When Z ¹ and Z ² are an alkenyl group having 2 carbon atoms and bonded to two adjacent carbon atoms, they may 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 bonded to two adjacent carbon atoms, they may 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 as or different from each other. In addition, Z ¹ and Z ³ may be the same as or different from each other, and Z ² and Z ⁴ may be the same or different from each other.

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

Z ¹ and Z ² may be bonded to two adjacent carbon atoms, and Z ³ and Z ⁴ may 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.} In addition, 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 .} Also, for example, ^{when both X 1} and X ² are hydrogen groups, ^{at least one of a combination of Z 1} and Z ² or a 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 a hydrogen group, a halo 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 is selected from the group consisting of ^{14 , and A 8} to A 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 It is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms and an alkoxy group.

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 in which A 9} is a hydrogen group.

[Formula 3]

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

In addition, the polymerization inhibitor may be included in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.08 moles, 0.0005 to 0.05 moles, or 0.001 to 0.05 moles based on 1 mole of the first sulfur compound.

Meanwhile, in the melt polymerization, a catalyst may be additionally used. The catalyst may be, for example, a nitrobenzene-based catalyst, and specifically, may be at least one selected from the group consisting of 1,3-diiod-4-nitrobenzene and 1-iod-4-nitrobenzene, but is not limited thereto. When the catalyst is used, it may be used in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.05 moles, or 0.0005 to 0.01 moles based on 1 mole of the first sulfur compound.

Melt polymerization may proceed under any conditions as long as the polymerization reaction of the composition including the diiodo aromatic compound and the first sulfur compound can be initiated. For example, melt polymerization may be carried out at a temperature of about 180 to 400 °C, 180 to 350 °C, or 180 to 300 °C, and at a pressure of about 0.001 to 500 torr, 0.001 to 450 torr, or 0.001 to 400 torr. . More specifically, melt polymerization may proceed under elevated temperature and reduced pressure reaction conditions. In this case, temperature rise and pressure drop are performed at an initial reaction condition of about 180 to 250° C. and a pressure of about 50 to 450 torr, which is the final reaction condition. It is changed to about 270 to 350° C. and pressure to about 0.001 to 20 torr, and may proceed for about 0.1 to 30 hours. More specifically, melt polymerization may be performed under the final reaction conditions at a temperature of about 280 to 300° C. and a pressure of about 0.1 to 2 torr.

Meanwhile, the order of mixing the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor is not particularly limited, but the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are simultaneously mixed, or the diiodo aromatic compound and a polymerization inhibitor may be mixed with a mixture including the first sulfur compound to prepare a composition for melt polymerization.

When 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, but may be determined in consideration of the final molecular weight of the target polyarylene sulfide. For example, about 0 to 30% by weight, 30 to 70% by weight, or 70 to 100% by weight of the diiodine aromatic compound contained in the initial reactant may be added at a time when the reaction is exhausted. Alternatively, the timing of the polymerization inhibitor may be added when the molecular weight of the polymerization product reaches a certain level. For example, the molecular weight of the polymerization reactant is 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% of the final molecular weight of the target polyarylene sulfide. % or more, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, a polymerization inhibitor may be added. The molecular weight of the polymerization reactant can be determined, for example, through gel permeation chromatography.

In addition, before the polymerization inhibitor is added, the composition including the diiodine aromatic compound and the first sulfur compound may be melt-mixed. In this case, a catalyst may also be included in the composition in the melt mixing step. The melt mixing is not particularly limited as long as all of the compositions can be melt-mixed, but for example, may be performed at a temperature of about 130 to 200°C or about 160 to 190°C. In the case of performing such melt mixing, melt polymerization to be performed later may be more easily performed.

First polyarylene sulfide resin post-processed with compatibilizer

The post-processed first polyarylene sulfide resin may be prepared by post-processing the first polyarylene sulfide resin using a compatibilizer.

In addition, the post-processed first polyarylene sulfide resin may include a first polyarylene sulfide resin; and end groups derived from compatibilizers.

The first polyarylene sulfide resin is as described above.

The compatibilizer for post-processing the first polyarylene sulfide resin may be a compound including a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group. Specifically, the compatibilizer may be one or more of the 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 a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ , 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 C1-C3 alkyl group, and a substituted or unsubstituted phenyl group, Z ^1' to Z ^{4 '} are each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms, and p ¹ and p ² are each independently an integer of 1 to 3, provided 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 bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring, and Z ³ ' and Z ⁴ ' are 2 carbon atoms When it is an alkylene group and is bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.

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

The substituted alkyl group having 1 or 2 carbon atoms or the substituted alkenyl group having 1 or 2 carbon atoms of ^{Z 1'} to Z ^{4' may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.}

One of B ¹ to B ⁷ may have a substituent of an alkyl group having 1 to 3 carbon atoms or a substituted phenyl group having 1 or 2 carbon atoms or a substituent of a phenyl group.

Z ¹ ′ and Z ² ′ may be bonded to two adjacent carbon atoms, and Z ³ ′ and Z ⁴ ′ may 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 a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ 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 1 to 5 carbon atoms. It is selected from the group consisting of an alkylene group and an alkoxy group, with the proviso that at least one of ^{Y 3} to Y ^{6 is -OB 8} , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ selected from the group consisting of Here, at least one of ^{Y 3} to Y ⁶ may be ^{—SB 9 in which B 9} is a hydrogen group.

[Formula 6]

Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ , 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, R ⁵ ' and R ⁶ ' are each independently selected from the group consisting of 1 to 5 carbon atoms It is an alkylene group.

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

The compatibilizer may perform a substitution reaction with an iodine atom that may be positioned at the terminal of the first polyarylene sulfide resin, or may serve as a compatibilizer by itself without a reaction. If the first polyarylene sulfide resin is post-processed with a compatibilizer, the atmosphere of the main chain and/or the terminal of the first polyarylene sulfide resin can be changed from hydrophobicity to hydrophilicity, and through this, other resins having hydrophilic functional groups and/or reactive groups , it is possible to improve the compatibility with inorganic fillers, etc., it is possible to improve the mechanical strength of the final product using the same and to significantly reduce the amount of outgas generated by heating.

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

The terminal group derived from the compatibilizer may mean a functional group of the compatibilizer. Specifically, the compatibilizer may be a compound containing a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group, so the terminal group derived from the compatibilizing agent is also carboxyl It may be a functional group such as a group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group.

More specifically, the terminal group derived from the compatibilizer may have a structure represented by one of the following Chemical Formulas 7 to 9.

[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 the same as described above.

The compatibilizer may be included 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. When the first polyarylene sulfide resin is post-processed using a compatibilizer after polymerization, the reaction efficiency of the compatibilizer is significantly better than when the same compound is added as a polymerization inhibitor during the polymerization of the resin. The content of the functional group can be maximized, and the target content of the functional group to be introduced into the final resin can be achieved through the compatibilizer while using a small amount of the compatibilizer. When the same compound is added as a polymerization inhibitor, the reaction efficiency is low because the compound is decomposed by a high-temperature environment required for the polymerization reaction or discharged during the reaction. Moreover, when added during polymerization of the first polyarylene sulfide resin, it is possible to minimize by-products that may be generated by the compatibilizer. Therefore, when the first polyarylene sulfide resin is post-processed with a compatibilizer, the amount of outgassing is reduced by reducing the amount of polymerization inhibitor / compatibilizer, which can be a cause of outgas, and by-products are minimized, and at the same time, compatibility is improved. Physical properties such as tensile strength, tensile elongation, and airtightness can be improved. In addition, the first polyarylene sulfide resin post-processed with a compatibilizer has an effect of reducing the production cycle as well as excellent cavity balance by improving processability in the injection process as the amount of outgas is reduced as described above. can

Post-processing using a compatibilizer may be performed by hot mixing. Hot mixing may be performed at a temperature of 290 to 330 °C. In addition, it can be carried out in a non-oxidizing atmosphere to achieve a high degree of polymerization while preventing the oxidative crosslinking reaction. In a non-oxidizing atmosphere, the oxygen concentration of the gas phase may be less than 5% by volume or less than 2% by volume, and more specifically, the gas phase may be substantially free of oxygen. In the case of post-processing through high-temperature mixing, iodine that may be partially present at the terminal of the first polyarylene sulfide resin is sufficiently removed and the crystallinity is excellent to reduce shrinkage, so the post-processed first polyarylene sulfide is used to The dimensional stability of the manufactured final article can be improved.

In addition, high-temperature mixing may be performed under a reactor capable of heating and stirring. For example, the reactor may be a reactor of various materials such as SUS. High-temperature mixing may be performed in a twin screw extruder, and the diameter ratio (L/D) of the twin screw extruder may be about 30 to 50. For example, the first polyarylene sulfide resin may be introduced through the main inlet of the twin-screw extruder, and other polymer materials such as thermoplastic resins or thermoplastic elastomers, fillers, etc. are separately provided through the side feeder located on the side of the extruder. can be put in The position of the side inlet may be about 1/3 to 1/2 from the outlet side of the entire barrel of the extruder, and through this, the filler and the like can be prevented from being broken by rotation and friction by the extruder screw in the extruder. In addition, the first polyarylene sulfide resin may be mixed with other additives added in a small amount before being added to the main inlet.

On the other hand, the post-processed first polyarylene sulfide resin is mainly composed of arylene sulfide units, but is usually derived from the first sulfur compound of the raw material, and the units according to the disulfide bond represented by [-SS-] are also the main chain can be included in The structural formula of the final polyarylene sulfide resin including a unit according to a disulfide bond may have the form of a copolymer suggested by Eastman (US Patent No. 47680000). The structural formula of the copolymer may be expressed as in Structural Formula 1 below.

[Structural formula 1] -(Ar-S)x-(Ar-S-S)y-

In the post-processed first polyarylene sulfide resin, when the sum of x corresponding to the arylene sulfide structure and y corresponding to the copolymer sulfide structure in Structural Formula 1 is 1, the content of x is 0.900 to 0.999, 0.950 to 0.999 or 0.990 to 0.999. . In addition, the disulfide bond fraction of the post-processed first polyarylene sulfide may be 0.001 to 10.0 wt%, specifically, 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, or 0.7 wt% or more, and 10.0 wt% or less , 5.0 wt% or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, 1.5 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 can In the present specification, the fraction (wt%) of disulfide bonds may be defined as the difference between the theoretical amount of sulfur in polyarylene sulfide and the amount of sulfur measured by elemental analysis with respect to the theoretical amount of sulfur in polyarylene sulfide.

[Equation 1]

Disulfide bond fraction (wt%) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (theoretical weight of sulfur in polyarylene sulfide)

The post-processed first polyarylene sulfide resin may include iodine derived from a diiodo aromatic compound, and the content of iodine is 100 to 10,000 ppm based on the total weight of the post-processed first polyarylene sulfide resin, specifically , 250 ppm or more, 500 ppm or more, 750 ppm or more, or 900 ppm or more, 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, 1900 ppm or less, 1,800 ppm or less, 1,700 ppm or less, 1,600 ppm or less, or 1,500 ppm or less.

The post-processed first polyarylene sulfide resin has a melt viscosity of 1 Pa·s or more, 10 Pa·s or more, 50 Pa·s or more, 100 Pa·s or more, 500 Pa·s or more, 1,000 Pa·s or more, 1,500 Pa s or more, 1,700 Pa s or more, 1,800 Pa s or more, 1900 Pa s or more, 2,000 Pa s or more, 2,100 Pa s or more, 2,100 Pa s or more, 2,200 Pa s or more, or 2,300 Pa s It may be s or more, and may be 7,000 Pa·s or less, 5,000 Pa·s or less, 4,000 Pa·s or less, 3,000 Pa·s or less, 2,500 Pa·s or less, 2,300 Pa·s or less, or 2,000 Pa·s or less. In the present specification, the melt viscosity is measured at 300° C. with a rotating disk viscometer, and when the viscosity is measured in an angular frequency section of 0.6 to 500 rad/s by a frequency sweep method, the viscosity at an angular frequency of 1.84 rad/s can be defined as

In addition, the nonlinearity index may be 0.001 or more, 0.01 or more, 0.05 or more, 0.09 or more, or 0.10 or more, and 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0,15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less or 0.10 or less. By adjusting the nonlinearity index within this range, the post-processed polyarylene sulfide resin can have improved processability and good cavity balance. The non-linearity index may be an index related to the molecular weight of the measurement target or molecular structure such as linear, branched, or cross-linked. Usually, when this value is close to 0, it indicates that the molecular structure of the resin is linear, and as this value increases, it indicates that many branched or crosslinked structures are included. In the present specification, the nonlinear index is measured at 300° C. with a rotating disk viscometer, and when the viscosity change rate in the shear rate section of ^{0.03 to 25 s −1 is measured by the frequency sweep method, it can be defined through Equation 2 below.}

[Equation 2]

Nonlinearity index = 1 - (melt viscosity at a shear rate of ^{17.3 s -1} ) / (melt viscosity at a shear rate of ^{3.22 s -1).}

The post-processed first polyarylene sulfide resin having a nonlinearity index in the above-described specific range is, for example, a method of solution polymerization of a mixture for melt polymerization including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor. In the present invention, it is possible to obtain this polyarylene sulfide resin by making it high molecular weight to some extent.

The post-processed first polyarylene sulfide resin may have a branching index (α) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, 0.60 or more, 0.61 or more, 0.62 or more, or 0.65 or more, 1.00 or less, 0.90 or less , 0.80 or less or 0.70 or less. In the present specification, α is calculated through the Mark-Howink equation represented by Equation 3 below. In general, the closer α is to 1, the more it is a linear polymer, and the closer it is to 0, the more it is a branched polymer.

[Equation 3]

[η] = KM ^α

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

In addition, the post-processed first polyarylene sulfide resin may have a melting point of 250 to 300 °C, 260 to 300 °C, 265 to 300 °C, or 270 to 290 °C. In the present specification, the melting point is measured using a differential scanning calorimeter (DSC) from 30°C to 320°C at a rate of 10°C/min, cooled to 30°C, and then from 30°C to 320°C again. It may be measured while the temperature is raised at a rate of 10 °C / min.

The post-processed first polyarylene sulfide resin may have a crystallization temperature of 150 to 300 °C, 200 to 250 °C, 210 to 240 °C, 215 to 230 °C, or 216 to 225 °C. When the crystallization temperature is increased, not only the crystallization rate is increased, but also the crystallinity is affected, so that the mechanical properties of the final composition can be improved. In the present specification, the crystallization temperature is increased at a rate of 10°C/min from 30°C to 320°C using a differential scanning calorimeter differential scanning calorimeter, cooled to 30°C, and then again from 30°C to 320°C at a rate of 10°C/min. It may be measured while raising the temperature to

The molecular weight of the post-processed first polyarylene sulfide resin may be measured by weight average molecular weight, number average molecular weight, peak peak molecular weight, and the like. The weight average molecular weight of the post-processed first polyarylene sulfide resin is not particularly limited as long as the effects of the present invention are not impaired, but in terms of mechanical strength, 25,000 g/mol or more, 30,000 g/mol or more, 40,000 g/mol or more Alternatively, it may be 50,000 g/mol or more, and may be 100,000 g/mol or less, 80,000 g/mol or less, 65,000 g/mol or less, or 55,000 g/mol or less in terms of cavity balance. In addition, in order to achieve excellent mechanical strength and good cavity balance, the weight average molecular weight of the post-processed first polyarylene sulfide resin is 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. The number average molecular weight is 1,000 g/mol or more, 5,000 g/mol or more, 7,500 g/mol or more, 9,000 g/mol or more, 10,000 g/mol or more, 11,000 g/mol or more, 12,000 g/mol or more, or 12,400 g/mol or more. g/mol or more, 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 peak molecular weight may be 10,000 g/mol or more, 15,000 g/mol or more, 20,000 g/mol or more, 25,000 g/mol or more, 27,000 g/mol or more, 27,900 g/mol or more, and 140,000 g/mol or less, 100,000 or more. g/mol or less, 75,000 g/mol or less, 50,000 g/mol or less, 45,000 g/mol or less, 43,000 g/mol or less, 35,000 g/mol or less, or 30,000 g/mol or less.

The amount of outgas of the post-processed 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 the present specification, the amount of outgas is quantified in wt% by using a gas chromatograph (GC) mass spectrometer to measure the amount of gas generated when a sample of a predetermined amount of polyarylene sulfide resin or resin composition is heated at 330° C. for 20 minutes. it could be

The terminal of the post-processed first polyarylene sulfide resin may include a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, a sulfonate group, and the like. Specifically, it may include a functional group derived from a compound represented by one of Formulas 4 to 6 described above.

The first polyarylene sulfide resin post-processed with a compatibilizer has excellent compatibility with other resins and inorganic fillers having a hydrophilic functional group and/or a reactive group, so the amount of outgas may be lower than that of polyarylene sulfide resin that is not post-processed, and also , compared to polyarylene sulfide resin prepared by using the same compound as a polymerization inhibitor during the polymerization of the resin, the amount of polymerization inhibitor / compatibilizer that can cause outgas can be lowered and by-products can be minimized. , the amount of outgas may be low.

In addition, although not being bound by a particular theory, as the amount of outgas is reduced as described above, the polyarylene sulfide resin post-processed with a compatibilizer improves processability in the injection process, thereby improving the cavity balance and reducing the production cycle. effect can be exhibited.

In addition, the first polyarylene sulfide resin post-processed with a compatibilizer may have excellent mechanical strength, such as tensile strength and tensile elongation, and airtightness as compatibility is improved.

additive

Additives are not limited as long as they do not impair the effects of the present invention, but specifically, fibrous reinforcement, inorganic filler, antioxidant, stabilizer, processing heat stabilizer, plasticizer, mold release agent, colorant, lubricant (滑)劑), a weathering stabilizer, a foaming agent, a rust inhibitor, a wax, a nucleating agent, other resin components, an anti-drip agent, an additional compatibilizer, and the like.

The fibrous reinforcement is, for example, glass fiber, PAN-based or pitch-based carbon fiber, silica fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, aluminum borate fiber, potassium titanate fiber, stainless steel, aluminum, titanium. , copper, and inorganic fibrous substances of metals such as pearls; and organic fibrous materials such as aramid fibers. Examples of the inorganic filler include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbesto, aluminasilicate, zeolite, and pyrophyllite; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; metal oxides such as alumina, magnesium oxide, silica, zirconia, titania, and iron oxide; glass beads; glass flakes; ceramic beads; boron nitride; silicon carbide; Calcium phosphate and the like. These fibrous reinforcing materials and inorganic fillers may be used individually or in mixture of 2 or more types.

Specifically, the glass fiber may be surface-treated to improve interfacial adhesion with the resin, and the surface treatment may be performed using an epoxy and a silane having an amino group. For example, the glass fiber may be an alumino-borosilicate glass. Further, the glass fibers may, for example, have an average diameter of 6 to 15 μm and an average length of 2 to 8 mm or 2 to 6 mm.

The heat stabilizer can be used to prevent the resin from decomposing due to the action of heat and light during the manufacturing process or use of the resin, and can be used in a high-temperature environment when mixing or molding polyarylene sulfide resin with other additives or resins. By minimizing the generated side reactions, the physical properties of the final polyarylene sulfide resin composition can be improved. Heat stabilizer is calcium magnesium zinc-based heat stabilizer, calcium zinc-based heat stabilizer, organotin-based heat stabilizer, metal ore-based heat stabilizer, barium zinc-based heat stabilizer, epoxy zinc-based heat stabilizer, magnesium aluminum carbonate-based heat stabilizer, zinc-based heat stabilizer and a metal-based thermal stabilizer such as a lead-based thermal stabilizer, and a non-metallic thermal stabilizer such as an epoxy-based thermal stabilizer and an organic phosphite-based thermal stabilizer. A commercially available thermal stabilizer includes CLC-120 from Dubon, a magnesium aluminum carbonate-based thermal stabilizer.

In addition, as the heat stabilizer, for example, a primary phenolic stabilizer, a secondary phosphorus stabilizer, and a primary and secondary mixed stabilizer may be used. It is preferred that the material has good thermal stability. In this regard, preferred stabilizers include ADEKA's AO-60, AO-80, Chemtura's Ultanox627A, 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 includes Mitsui's Hi-Wax ^TM .

The nucleating agent can be used to accelerate the crystallization rate, and by using the nucleating agent, the crystallinity can be increased even in a low-temperature mold to improve the surface properties of the resin. The nucleating agent may be an inorganic material having high temperature thermal stability, and may include talc, calcium silicate, silica, boron nitride, and the like. Specifically, boron nitride may be in the form of a hexagonal system, and the purity may be one having a B ₂ O ₃ content of 0.5 wt % or less based on the total weight of boron nitride. Alternatively, boronitride having a purity of 95% by weight or more may be used.

In addition, other resins may be included in an appropriate amount according to the properties required for the first polyarylene sulfide resin. Here, the resin component is, for example, ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) acrylonitrile of a monomer homopolymers or copolymers; polyesters such as polyurethane, polybutylene terephthalate, and polyethylene terephthalate; polyacetal; polycarbonate; polysulfone; polyallyl sulfone; polyethersulfone; polyphenylene ether; polyether ketone; polyether ether ketone; polyimide; polyamideimide; polyetherimide; silicone resin; epoxy resin; phenoxy resin; liquid crystal polymer; polyaryl ether; It may be a homopolymer such as a random copolymer or block copolymer, a graft copolymer, and the like.

Specifically, the other resin components may include an elastomer to improve impact strength, and the elastomer is a polyvinyl chloride-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, and a polybutadiene-based elastomer. and a terpolymer of glycidyl methacrylate and methyl acrylic ester.

In addition, the other resin component may include a thermoplastic elastomer (TPE). Thermoplastic elastomers are specifically thermoplastic polyether block amides (TPA), thermoplastic polyurethane elastomers (TPU), thermoplastic copolyester elastomers (TPC), styrene block copolymer-based thermoplastic elastomers (TPS), thermoplastics and vulcanization. It may be a thermoplastic elastomer (TPV) made of an elastomer, or the like. The thermoplastic elastomer may be an epoxy elastomer including an epoxy functional group, such as a copolymer of ethylene and glycidyl methacrylate. A commercially available thermoplastic elastomer is Sumimoto's IGETABOND ^® BF-E.

The anti-drip agent may be used to prevent dripping when the polyarylene sulfide resin composition is burned. The anti-drip agent may include a fluorine-based anti-drip agent. Specifically, the anti-drip agent is a fluorine-based resin (polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, etc.), perfluoroalkanesulfonic acid alkali metal salt compound (perfluoromethanesulfonic acid sodium salt, perfluoro -n-butanesulfonate potassium salt, perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonate sodium salt, perfluoro-2-ethylhexanesulfonate calcium salt, etc.), perfluoroalkanesulfonate It may include an alkaline earth metal salt of phonic acid, and more specifically, it may include polytetrafluoroethylene. Commercially available anti-drip agents include Hannanotech's FS-100, FS-200, and FS-300.

The additional compatibilizer means a compatibilizer additionally included in the polyarylene sulfide resin composition in addition to the compatibilizer used for post-processing the first polyarylene sulfide resin. Specifically, the additional compatibilizer may be a compatibilizer other than the compound represented by one of Formulas 4 to 6. For example, the additional compatibilizer may be an epoxy silane-based compatibilizer, and commercially available additional compatibilizers include Silquest ^® A-186 and A-187 from Momentive Performance Materials.

In addition, the metallic additive can promote the compatibilization reaction between the polyarylene sulfide resin and the thermoplastic elastomer, especially when used with a thermoplastic elastomer. Zinc salts, magnesium salts, calcium salts, sodium salts, lithium salts, etc. can be used as these metallic additives, and they are thermally stable and help the reaction between the glycidyl functional group of the elastomer and the compatible functional group of the polyarylene sulfide resin. It is desirable to be able to give Preferred metallic additives meeting this requirement include zinc stearate (Sigma Aldrich-307564), calcium stearate (Sigma Aldrich-26411), magnesium acetate (Sigma Aldrich-228648), magnesium stearate salt (Sigma Aldrich). -415057), sodium stearate (Sigma-Aldrich-S3381), and lithium carbonate (Sigma-Aldrich-203629).

The additive may specifically include at least one selected from the group consisting of a fibrous reinforcement, a heat stabilizer, and an elastomer, and specifically, the additive may include a heat stabilizer. More specifically, the additive may include glass fibers or include an elastomer and a heat stabilizer.

Post-processed first polyarylene sulfide resin composition

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

Specifically, the post-processed first polyarylene sulfide resin composition contains 0.1 wt% or more, 1 wt% or more of the post-processed first polyarylene sulfide resin based on the total weight of the post-processed first polyarylene sulfide resin composition , 2% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, or 60% by weight or more; , 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less can be included as

On the other hand, the post-processed first polyarylene sulfide resin composition, based on the total weight of the post-processed first polyarylene sulfide resin composition, 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 45% by weight or less or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less.

More specifically, the post-processed first polyarylene sulfide resin composition comprises 10 to 70 wt%, 10 to 60 wt%, 10 to 50 wt% of glass fibers based on the total weight of the post-processed first polyarylene sulfide resin composition. weight percent, 15 to 45 weight percent, 20 to 40 weight percent, or 25 to 35 weight percent, and 0.1 to 20 weight percent, 1 to 20 weight percent, 5 to 15 weight percent, or 7 to 35 weight percent elastomer. It may be included in 10% by weight. In addition, the heat stabilizer may be included in an amount of 0.01 to 5% by weight, 0.01 to 2% by weight, or 0.05 to 1% by weight on the same basis.

In addition, the post-processed first polyarylene sulfide resin composition includes 10 to 70% by weight of glass fibers based on the total weight of the post-processed first polyarylene sulfide resin composition, or 0.1 to 0.1 to each of an elastomer and a heat stabilizer It may be included in 20% by weight and 0.01 to 5% by weight.

The post-processed first polyarylene sulfide resin composition, compared to the first polyarylene sulfide resin composition that is not post-processed with a compatibilizer, maintains a good amount of outgas, and has excellent airtightness, cavity balance, and mechanical strength. .

[Polyarylene Sulfide Mixed Resin Composition]

According to an embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and an additive, a resin composition for a gasket (hereinafter, polyarylene sulfide mixed resin composition) is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; preparing a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; and an additive, and mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin.

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

Second polyarylene sulfide resin

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

The second polyarylene sulfide resin is not particularly limited as long as it is prepared including solution polymerization of a dihalo aromatic compound and a second sulfur compound. As a commercial method for preparing such a polyarylene sulfide resin, a Macallum process of solution polymerization of p-dichlorobenzene and sodium sulfide in the presence of a polar organic solvent such as N-methyl pyrrolidone (Macallum process) This is known A typical process is described in US Pat. No. 2,513,188.

The melt polymerization may be performed in the presence of an organic polar solvent. The organic polar solvent is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam. , N-propylcaprolactam, N-methylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolinone, N-ethyl-2-pyrrolidinone, N-isopropyl-2-pyrrolidinone , N-Isobutyl-2-pyrrolidinone, N-propyl-2-pyrrolidinone, N-butyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-3-methyl -2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-2-piperidone, N-methyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo-hexamethyleneimine , hexamethyl phosphate triamide, hexaethyl phosphate triamide, tetramethyl urea, 1,3-dimethylethylene urea, 1,3-dimethylethylene urea, 1,3-dimethylpropylene urea, 1-methyl-1-oxosulfolane , 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-methyl-1-oxophosphane, 1-propyl-1-oxophosphane and 1-phenyl-1-oxophosphane It may be at least one selected from the group consisting of. The organic polar solvent may be, for example, N-methylpyrrolidone.

The dihalo aromatic compound refers to a compound having an aromatic ring and two halo groups directly bonded thereto. Here, the halogen atom of the halo group may be each atom of fluorine, chlorine, bromine and iodine, and two halo groups present in the dihalo aromatic compound may be the same or different from each other. More specifically, both halogen atoms may be chlorine. Dihalo aromatic compounds include, for example, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl It may be at least one selected from the group consisting of ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide and dihalodiphenylketone. The dihalo aromatic compound may be, for example, 1,4-dichlorobenzene, but is not particularly limited thereto.

The second sulfur compound may be at least one selected from the group consisting of an alkali metal sulfide and an alkali metal sulfide-forming compound capable of forming the alkali metal sulfide. In addition, the second sulfur compound may be at least one selected from the group consisting of alkali metal hydrosulfide and the alkali metal hydrosulfide-forming compound. The second sulfur compound includes, for example, alkali metal hydrosulfides such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide, and alkali metal hydrosulfides such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. It may be a metal sulfide, but is not particularly limited thereto. The alkali metal sulfide-forming compound or the alkali metal hydrosulfide-forming compound may be, for example, hydrogen sulfide. By blowing hydrogen sulfide into alkali metal hydroxide (eg NaOH), alkali metal hydrosulfide (eg NaSH) or alkali metal sulfide (eg Na ₂ S) can be formed. The second sulfur compound may be at least one selected from the group consisting of anhydrides, hydrates, and aqueous solutions. The second sulfur compound may be, for example, sodium sulfide hydrate, but is not particularly limited thereto.

Polyarylene sulfide mixed resin composition

The resin composition for the gasket may include the first polyarylene sulfide resin, the second polyarylene sulfide resin, and an additive.

The solution-polymerized polyarylene sulfide resin, which is prepared by solution polymerization of a dihalo aromatic compound and a sulfur compound, has excellent physical properties such as a high crystallization temperature and mechanical strength, but is out due to the use of a solvent that can cause outgas It has a disadvantage in that the amount of gas is high, and thus the cavity balance is low. On the other hand, the melt-polymerized polyarylene sulfide resin, which is prepared by melt polymerization of a mixture containing a diiodo aromatic compound, a sulfur compound, and a polymerization inhibitor, has a remarkably low amount of outgas, but a disulfide bond with a weak structure due to the manufacturing method. It has a disadvantage in that mechanical strength is low as it is included.

However, the present inventors surprisingly found that by mixing the solution-polymerized polyarylene sulfide resin and the melt-polymerized polyarylene sulfide resin, the amount of outgas is low at a level comparable to that of the melt-polymerized polyarylene sulfide resin, and the cavity balance is excellent while , discovered that a polyarylene sulfide mixed resin composition having mechanical strength and airtightness comparable to or superior to that of a solution-polymerized polyarylene sulfide resin can be prepared.

The effect of the mixed resin composition is not limited to a specific theory, but may be achieved by reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the terminal halogen of the second polyarylene sulfide. can do. Accordingly, the disulfide bond, which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This can be significantly reduced.

Mixing of the first polyarylene sulfide resin, the second polyarylene sulfide resin, and the additive may be performed through melt mixing. Melt mixing may be performed under any conditions as long as the first polyarylene sulfide resin and the second polyarylene sulfide resin can be melted. For example, melt mixing may be performed in a single-screw or twin-screw kneader and extruder, a polymerization reactor, a kneader reactor, and the like. More specifically, melt mixing may be performed in a twin-screw extruder, and may be performed at a temperature of 280 to 330°C, preferably 290 to 310°C. In this case, the discharge amount 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. It is preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of a resin component and the screw rotation speed (rpm) is especially 0.08-0.14 kg/hr*rpm. By degassing in a reactor equipped with a vacuum line during the mixing, a polyarylene sulfide mixed resin with a further reduced amount of outgas can be prepared.

The polyarylene sulfide mixed resin composition contains the first polyarylene sulfide resin in 0.1 wt% or more, 1 wt% or more, 2 wt% or more, 5 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition, 10 It may include at least 15 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 60 wt%, or at least 70 wt%, 99.9 Weight % 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 Weight % or less, 60 wt% or less, 55 wt% or less, or 50 wt% or less may be included.

In addition, the polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 0.1 wt% or more, 1 wt% or more, 2 wt% or more, 5 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition. , 10% by weight or more, 15% by weight or more, or 20% by weight or more, 99.9% by weight or less, 99% by weight or less, 90% by weight or less, 70% by weight or less, 50% by weight or less, 42% by weight or less , 40% by weight or less, 38% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less.

In addition, the polyarylene sulfide mixed resin composition may include 10 to 99.9 wt% of the first polyarylene sulfide resin and the second polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin composition, More specifically, it may be included in an amount of 20 to 99% by weight, 30 to 99% by weight, 30 to 95% by weight, 30 to 70% by weight, or 50 to 70% by weight.

The polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 30% by weight or less, specifically 0.0001 to 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It may be included in % by weight, more specifically, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, and 25% by weight or less, 20% by weight or more It may be included in an amount of 15% by weight or less, 10% by weight or less, or 5% by weight or less. When the second polyarylene sulfide resin is included in the above range, the effect by mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin becomes significant, the amount of outgas is reduced, and the cavity balance and tensile elongation are improved can be

In addition, the polyarylene sulfide mixed resin composition contains an additive in an amount of 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, 10 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition, 20% by weight or more or 30% by weight or more, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less may be included.

More specifically, the polyarylene sulfide mixed resin composition contains 10 to 70% by weight, 10 to 60% by weight, 10 to 50% by weight, 15 to 45% by weight of glass fibers, based on the total weight of the polyarylene sulfide mixed resin composition. weight percent, 20 to 40 weight percent, or 25 to 35 weight percent, and 0.1 to 20 weight percent, 1 to 20 weight percent, 5 to 15 weight percent, or 7 to 10 weight percent elastomer. can In addition, the heat stabilizer may be included in an amount of 0.01 to 5% by weight, 0.01 to 2% by weight, or 0.05 to 1% by weight on the same basis.

In addition, the polyarylene sulfide mixed resin composition contains 10 to 70% by weight of glass fibers based on the total weight of the polyarylene sulfide mixed resin composition, or 0.1 to 20% by weight and 0.01 to 20% by weight of an elastomer and a heat stabilizer, respectively It may be included in 5% by weight.

On the other hand, the polyarylene sulfide mixed resin means a resin composed of the first polyarylene sulfide and the second polyarylene sulfide, and the melt viscosity, non-linearity index, branching index (α), molecular weight of the polyarylene sulfide mixed resin And the melting point is the same as described above for the post-processed first polyarylene sulfide resin.

In addition, the polyarylene sulfide mixed resin may have a disulfide bond fraction of 0.001 to 10.0% by weight, specifically, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, or 1.0% by weight or more, and 10.0 Weight % or less, 5.0 wt% or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, or 1.4 wt% or less.

The polyarylene sulfide mixed resin may contain iodine derived from a diiodo aromatic compound, and the content of iodine is 1 to 10,000 ppm, specifically, 5 ppm or more, based on the total weight of the polyarylene sulfide mixed resin; 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 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, It may be 3,000 ppm or less, 2,500 ppm or less, 2,300 ppm or less, 2,000 ppm or less, 1,900 ppm or less, or 1,800 ppm or less.

The crystallization temperature of the polyarylene sulfide mixed resin may be as high as that of the second polyarylene sulfide resin. For example, the polyarylene sulfide mixed resin may have a crystallization temperature 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. When the crystallization temperature of the polyarylene sulfide mixed resin is increased, not only the crystallization rate is increased, but also the crystallinity is affected, so that the mechanical properties of the final composition including the resin can be improved.

The amount of outgas of the polyarylene sulfide mixed resin may be 0.001 to 5% by weight, and specifically, 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, or 0.35% by weight or more. % or more, 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, It may be 0.8 wt% or less, 0.6 wt% or less, or 0.5 wt% or less.

This polyarylene sulfide mixed resin composition has a low outgas amount comparable to that of the first polyarylene sulfide resin composition and has excellent cavity balance, and has a tensile strength comparable to or superior to that of the second polyarylene sulfide resin composition; It may have tensile elongation and airtightness.

[Post-processed polyarylene sulfide mixed resin composition]

According to an embodiment, the first polyarylene sulfide resin is post-processed in which terminal groups derived from a compatibilizer are introduced into the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and an additive, a resin composition for a gasket is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; preparing a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; mixing an additive, the first polyarylene sulfide resin and the second polyarylene sulfide resin; and post-processing the first polyarylene sulfide resin using a compatibilizer.

The post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives are the same as described above.

Post-processed polyarylene sulfide mixed resin composition

The resin composition for the gasket may include the post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives (hereinafter, post-processed polyarylene sulfide mixed resin composition). Their mixing is as described above.

However, post-processing of the first polyarylene sulfide resin may be performed before mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin, may be performed with mixing, or may be performed after mixing have. In addition, it may be carried out before mixing and additionally performed with or after mixing, and other combinations are possible without limitation. For example, post-processing of the first polyarylene sulfide resin is performed by adding a compatibilizer to the twin-screw extruder when the first polyarylene sulfide resin and the second polyarylene sulfide resin are put into a twin-screw extruder and melt-mixed. can At this time, the conditions can be set so that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of the resin component and the screw rotation speed (rpm) of the twin screw extruder becomes 0.02-0.2 kg/hr·rpm.

The terminal of the post-processed polyarylene sulfide mixed resin may include a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.

The post-processed polyarylene sulfide mixed resin composition comprises 0.1 wt% or more, 1 wt% or more, 2 wt% or more, based on the total weight of the post-processed first polyarylene sulfide resin, post-processed polyarylene sulfide mixed resin composition, 5% or more, 10% or more, 15% or more, 20% or more, 30% or more, 40% or more, 45% or more, 50% or more, 60% or more, or 70% or more 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% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, or 50% by weight or less.

In addition, the post-processed polyarylene sulfide mixed resin composition comprises 0.1 wt% or more, 1 wt% or more, 2 wt% or more, based on the total weight of the post-processed polyarylene sulfide mixed resin composition of the second polyarylene sulfide resin; 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, 99.9% by weight or less, 99% by weight or less, 90% by weight or less, 70% by weight or less, 50% by weight 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, 20 wt% or less, 15 wt% or less, or 10 wt% or less.

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

The post-processed polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 30% by weight or less, based on the total weight of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin, specifically as 0.0001 to 30% by weight, more specifically, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, and 25% by weight or less , 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less. When the second polyarylene sulfide resin is included in the above range, the effect of mixing the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin becomes significant, and the amount of outgas decreases, cavity balance, and tensile strength and tensile elongation may be improved.

In addition, the post-processed polyarylene sulfide mixed resin composition contains an additive of 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, 10 based on the total weight of the post-processed polyarylene sulfide mixed resin composition It may include at least 20 wt%, or at least 30 wt%, 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 more, 20 wt% or more, or 30 wt% or more Weight % or less, 30 wt% or less, 20 wt% or less, or 15 wt% or less may be included.

More specifically, the post-processed polyarylene sulfide mixed resin composition contains 10 to 70 wt%, 10 to 60 wt%, and 10 to 50 wt% of glass fibers based on the total weight of the post-processed polyarylene sulfide mixed resin composition. , 15 to 45 wt%, 20 to 40 wt%, or 25 to 35 wt% of the elastomer, 0.1 to 20 wt%, 1 to 20 wt%, 5 to 15 wt%, or 7 to 10 wt% % can be included. In addition, the heat stabilizer may be included in an amount of 0.01 to 5% by weight, 0.01 to 2% by weight, or 0.05 to 1% by weight on the same basis.

In addition, the post-processed polyarylene sulfide mixed resin composition may contain 10 to 70% by weight of glass fibers based on the total weight of the post-processed polyarylene sulfide mixed resin composition, or 0.1 to 20% by weight of an elastomer and a heat stabilizer, respectively % and may be included in an amount of 0.01 to 5% by weight.

On the other hand, the post-processed polyarylene sulfide mixed resin means a resin composed of the post-processed first polyarylene sulfide and the second polyarylene sulfide, and the melt viscosity, non-linearity index, and branching of the post-processed polyarylene sulfide mixed resin Index (α), molecular weight, melting point, disulfide bond fraction, iodine content, crystallization temperature, and outgas amount are the same as described above for the polyarylene sulfide mixed resin.

The post-processed polyarylene sulfide mixed resin composition has a low outgas amount comparable to that of the first polyarylene sulfide resin composition and has excellent cavity balance, while the first polyarylene sulfide resin composition and the second polyarylene sulfide It can exhibit superior mechanical strength and airtightness than all of the resin compositions.

This effect is not limited to a specific theory, but may be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the terminal halogen of the second polyarylene sulfide. can do. Accordingly, the disulfide bond, which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This can be significantly reduced.

Furthermore, since the first polyarylene sulfide resin is post-processed using a compatibilizer, compatibility with other resins and inorganic fillers having hydrophilic functional groups and/or reactive groups is improved, and the mechanical properties of the final article manufactured using the mixed resin Strength can be improved and the amount of outgas generated by heating can be significantly reduced. In addition, the reaction efficiency of the compatibilizer is significantly superior to that of adding the same compound 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. The target content of functional groups to be introduced into the final resin can be achieved through the compatibilizer. Therefore, in the case of post-processing with a compatibilizer, the amount of outgas is further increased by lowering the amount of polymerization inhibitor / compatibilizer that can be a cause of outgas, and minimizing byproducts that can be generated by the compatibilizer in a high-temperature environment required for polymerization reaction. reduced, and at the same time, compatibility is improved, so that not only the cavity balance is excellent, but also physical properties such as tensile strength, tensile elongation, and airtightness can be improved.

[Gasket]

According to one embodiment, there is provided a gasket for a secondary battery comprising a resin composition for the gasket.

According to another embodiment, the exterior body having an opening; a sealing body sealing the opening of the exterior body; a positive electrode plate, a negative electrode plate, and an electrolyte provided inside the exterior body; a separator provided between the positive electrode plate and the negative electrode plate; a positive electrode terminal electrically connected to the positive electrode plate; a negative terminal electrically connected to the negative electrode plate; A secondary battery is provided, including the above-described gasket for secondary battery in contact with the positive terminal or the negative terminal.

The resin composition for the gasket includes the above-described first polyarylene sulfide resin, post-processed first polyarylene sulfide resin, second polyarylene sulfide resin, polyarylene sulfide mixed resin, or post-processed polyarylene sulfide mixed resin. may include.

In addition, the gasket for a secondary battery may be a molded article in which the resin composition for the gasket is molded. The resin composition for the gasket may be molded in various methods and shapes without limitation. Typically, the resin composition may be cut into pellets, and by supplying these pellets to a molding machine and melt molding, a molded article having a desired shape can be finally obtained. Melt molding may be, for example, injection molding, extrusion molding, compression molding, or the like, and specifically may be injection molding. The mold temperature during injection molding may be about 50 ° C. or more, 60 ° C. or more, or 80 ° C. or more in consideration of crystallization, and about 190 ° C. or less, 170 ° C. or less, or 160 ° C. or less in consideration of the deformation of the specimen. The molding may be in various forms such as films, sheets, and fibers.

The above-described resin composition for a gasket has good airtightness as well as excellent cavity balance and mechanical strength. , it can be usefully used as a secondary battery gasket.

[Production Example]

1. First polyarylene sulfide resin

Preparation a1: Preparation of PPS a1

A thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of filling nitrogen and applying a vacuum were attached to the 5 L reactor, and 5,240 g of paradiiodobenzene and 450 g of elemental sulfur were added to the reactor. After heating the composition in the reactor containing paradiiodobenzene and elemental sulfur to 180° C. to completely melt and mix it, starting from the initial reaction conditions of a temperature of 220° C. and a pressure of 350 torr, the temperature is gradually increased and reduced, and the temperature is 300° C. And the polymerization reaction was carried out under the final reaction conditions of a pressure of 1 torr or less. When 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 product reached about 15,000 g/mol, diphenyl as a polymerization inhibitor was added to the reactor. 24 g of disulfide (Sigma-Aldrich-169021) was added and the reaction was carried out for 1 hour, then the reaction was further proceeded for 1 hour by gradually reducing the pressure to a pressure of 0.5 torr or less, and then the reaction was terminated. PPS a1 was prepared as a first polyarylene sulfide resin by processing it into pellets using a cutter.

Preparation a2: Preparation of PPS a2

In the same manner as in Preparation Example a1, except that 4.5 g of 2,2'-dithiodibenzoic acid (Sigma-Aldrich-43761, purity of 95.0% or more) was used instead of 24 g of diphenyldisulfide as a polymerization inhibitor, the first polyaryl About 1,500 g of PPS a2 was prepared as a ren sulfide resin.

2. Second polyarylene sulfide resin

Preparation b: Preparation of PPS b

3,027 g of sodium sulfide pentahydrate and 5,400 g of NMP as a polar organic solvent were added to the reactor, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Next, a solution in which 2,646 g of para-dichlorobenzene and 17.01 g of parachlorobenzoic acid were dissolved in 2,070 g of NMP was put into the reactor, and the polymerization reaction was carried out at 220 to 240° C. for 8 to 12 hours under a nitrogen atmosphere. After cooling the reactor, the polymerization product was taken out and filtered. The filtered cake was further washed with 2,880 g of NMP, and 10 L of ion-exchanged water was added to the cake containing NMP, which was then stirred in an autoclave at 200° C. for 10 minutes, followed by further filtration. The final filtered cake was dried at 130° C. for 3 hours to prepare PPS b as a second polyarylene sulfide resin.

3. Post-processed first polyarylene sulfide resin

Preparation c1: 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 2,2'-dithiodibenzoic acid (Sigma-Aldrich-43761, purity 95.0% or more) as a compatibilizer 0.3 weight After putting the part (4.5 g) into a twin-screw kneading extruder, melt blending was performed 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 a post-processed first polyarylene sulfide resin.

Preparation c2: Preparation of PPS c2

Except that 0.3 parts by weight of 4,4'-dithiodianiline (Sigma-Aldrich-369462, purity 98% or more) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, the same procedure as in Preparation c1 was carried out , PPS c2 was prepared as a post-processed first polyarylene sulfide resin.

Preparation c3: Preparation of PPS c3

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

Preparation c4: Preparation of PPS c4

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

Preparation c5: Preparation of PPS c5

Preparation c1 except that 0.3 parts by weight of 3-(triethoxysilyl)propane-1-thiol (Power chemical (China) SiSiB-PC2310) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer In the same manner as described above, PPS c5 was prepared as the post-processed first polyarylene sulfide resin.

Preparation c6: Preparation of PPS c6

As a compatibilizer, 0.3 parts by weight of 1,2-bis(3-(triethoxysilyl)propyl)disulfane (Power chemical (Chinese company) SiSiB-PC2200) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid Except that, in the same manner as in Preparation Example c1, PPS c6 was prepared as a post-processed first polyarylene sulfide resin.

4. Polyarylene sulfide resin composition

The first polyarylene sulfide resin, the second polyarylene sulfide resin, and the post-processed first polyarylene sulfide resin prepared according to the above-described preparation example were mixed in a twin-screw kneading extruder (Toshiba Group) in the weight ratios shown in Tables 1 to 5 below. A polyarylene sulfide resin composition (composition prior to mixing of additives) was prepared by melt-kneading at 300° C. at 300° C. (manufactured by Kai Co., Ltd., TEM-35B), and processing it into pellets using a small strand cutter. Thereafter, the polyarylene sulfide resin composition was uniformly mixed using a tumbler at the weight ratios shown in Tables 1 to 5 together with glass fiber, elastomer and heat stabilizer, and a twin-screw kneading extruder (manufactured by Toshiba Kikai Co., Ltd., TEM-35B) was melt-kneaded at 300° C., and then processed into pellets using a small strand cutter to prepare a polyarylene sulfide resin composition (composition after mixing with additives).

Specifically, PPS A1-1 to A2 as the first polyarylene sulfide resin composition, PPS B1 and B2 as the second polyarylene sulfide resin composition, and PPS C1-1 to C2 as the post-processed first polyarylene sulfide resin composition , PPS D1-1 to D2-5 as a polyarylene sulfide mixed resin composition, and PPS E1-1 to E2-4 as a post-processed polyarylene sulfide mixed resin composition were obtained.

The glass fiber, the elastomer and the heat stabilizer are specifically shown in Table 6 below.

[Experimental example]

In the polyarylene sulfide resin composition prepared according to the preparation example, the melting point, crystallization temperature, melt viscosity, nonlinear index, molecular weight, branching index, disulfide bond fraction, outgas amount and iodine content were measured for the composition before mixing with additives It was derived, and with respect to the composition after mixing the additives, outgas amount, cavity balance, tensile strength, tensile elongation and airtightness were measured/evaluated by the following methods, and are shown in Tables 7 to 13 below.

(1) Melting point (Tm) and crystallization temperature (Tc)

Using TA instrument's Q20 model differential scanning calorimeter (DSC), the temperature was raised from 30°C to 320°C at a rate of 10°C/min, and after cooling to 30°C at a rate of 10°C/min, The melting point and crystallization temperature were measured again while the temperature was raised from 30°C to 320°C at a rate of 10°C/min.

(2) melt viscosity (MV) and non-linearity index

Melt viscosity is, when the viscosity is measured in the frequency range of 0.6 to 500 rad/s by a frequency sweep method at 300° C. with a rotating disk viscometer, the viscosity at each frequency condition of 1.84 rad/s has been defined

The nonlinear index was calculated through Equation 2 below.

[Equation 2]

Nonlinearity index = 1 - (melt viscosity at a shear rate of ^{17.3 s -1} ) / (melt viscosity at a shear rate of ^{3.22 s -1).}

(3) number average molecular weight (Mn), weight average molecular weight (Mw) and peak peak molecular weight (Mp)

The number average molecular weight, weight average molecular weight, and peak peak molecular weight of the polyarylene sulfide resin composition were measured by gel permeation chromatography under the following measurement conditions. For all molecular weight measurements, six types of monodisperse polystyrene were used for calibration.

[Gel Permeation Chromatography Measurement Conditions]

Device: Agilent PL-220

Column: Agilent, PLgel pore size 105 Å + 104 Å + 500 Å + 50 Å (4 columns)

Column temperature: 210°C

Solvent: 1-chloronaphthalene

Measurement method: triple system detector (RI, viscometer, light scatter 15° and 90°)

(4) branch ratio (α)

The branching index was defined as an α value calculated by applying the viscosity measured from the triple system detector to the Mark-Howink equation of Equation 3 below. The Mark Howink equation is a relationship between molecular weight and intrinsic viscosity of a polymer, and the branching index (α) indicates the degree of branching of the polymer. That is, the closer α is to 1, the more linear the polymer, and the closer to 0, the more branched the polymer is.

[Equation 3]

[η] = KХM ^α

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

(5) fraction of disulfide bonds (-S-S-)

The binding fraction of disulfide was calculated through Equation 1 below.

[Equation 1]

Disulfide bond fraction (wt%) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (theoretical weight of sulfur in polyarylene sulfide)

(6) Outgas volume

Composition before mixing of additives: The amount of gas generated by heating a predetermined amount of a sample of the polyarylene sulfide resin composition at 330° C. for 20 minutes was quantified in weight % using a gas chromatograph (GC) mass spectrometer.

Composition after mixing of additives: A sample of a predetermined amount of the polyarylene sulfide resin composition was heated at 325° C. for 15 minutes, and the amount of gas generated was quantified in weight % using a gas chromatograph (GC) mass spectrometer.

(7) Iodine content

The iodine content of the polyarylene sulfide resin composition was measured by ion chromatograph (IC) using IC (AQF) Thermo Scientific, ICS-2500 (Mitsubishi AQF-100).

(8) Cavity balance

The polyarylene sulfide resin composition was injection molded using a washer mold having 40 cavities under the minimum molding conditions in which the cavity (C1) closest to the primary spool was completely filled. Molding conditions were set to a 75-ton molding machine, a cylinder 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) furthest from the primary spool was calculated as the weight ratio of the molded part of the cavity (C1) to the molded part of the cavity (C1) . Since it can be said that the cavity balance is excellent as the filling degree of the cavity C10 is high, the cavity balance of each polyarylene sulfide resin composition was evaluated based on the following criteria based on the filling degree.

AA: 90% by weight or more

A: 80% by weight or more and less than 90% by weight

B: 70% by weight or more and less than 80% by weight

C: 60% by weight or more and 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) confidentiality

After processing the polyarylene sulfide resin composition into a box-shaped molded article of 8 mm (length) * 8 mm (width) * 10 mm (thickness), and after injecting the electrolyte into the molded article, 8 used in the compressive stress relaxation test A sample for airtightness test sealed with a constant stress (under 10% strain) with a flat plate of mm (length) * 8 mm (width) * 3 mm (thickness) was prepared. Here, the electrolyte is a solution in which LiPF ₆ is dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1:1) at a concentration of 1 mol/L. The sample for airtightness test was left for 100 hours under dry heat at 60° C., and the degree of leakage of the electrolyte was checked, and the results were evaluated according to the following criteria.

○: No leakage of electrolyte after 100 hours

X: Electrolyte leakage occurs after 100 hours

Post-processed first polyarylene sulfide resin composition

As can be seen from the above table, PPS C1-1 to C1-9 containing the first polyarylene sulfide resin and additives post-processed with a compatibilizer, while maintaining a good amount of outgas, the first polyarylene that is not post-processed with a compatibilizer Compared to A1-2 containing the first polyarylene sulfide resin and additive prepared by using PPS A1-1 containing a sulfide resin and an additive and a compound of Formula 4 as a polymerization inhibitor, the cavity balance, tensile strength, tensile elongation and It was confirmed that all of the confidentiality was excellent.

As can be seen in the table above, PPS C2 including the first polyarylene sulfide resin and additives post-processed with a compatibilizer includes a first polyarylene sulfide resin and additives that are not post-processed with a compatibilizer while maintaining a good amount of outgas It was confirmed that the cavity balance, tensile strength, tensile elongation, and airtightness were all superior to that of PPS A2.

Polyarylene sulfide mixed resin composition

As can be seen from the above table, PPS D1-1 to D1-3 and D1-6 to D1-8 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and additives are the first polyarylene Compared to PPS A1-1 containing a sulfide resin and additives, the cavity balance, tensile strength, tensile elongation and airtightness are excellent, and compared to PPS B1 containing the second polyarylene sulfide resin and additives, the outgas amount, cavity balance and It was confirmed that the tensile elongation was excellent.

However, PPS D1-7 and D1-8 containing an elastomer as an additive had somewhat lower tensile strength than PPS D1-1 to PPS D1-6, but still higher than PPS A1-1, and PPS A1-1 and the tensile elongation was significantly higher than that of PPS B1.

Furthermore, PPS D1-1 to D1-3 and D1-6 to D1-8 are the content of the second polyarylene sulfide resin based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It was confirmed that the outgas amount, cavity balance, and tensile elongation were significantly superior to those of PPS D1-4 and D1-5, which were more than 30% by weight.

As can be seen in the table above, PPS D2-1 to D2-3 and D2-5 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive are the first polyarylene sulfide resin and the additive. Compared to PPS A2-1 containing was able to confirm

Moreover, in PPS D2-1 to D2-3 and D2-5, the content of the second polyarylene sulfide resin is greater than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It was confirmed that the amount of outgas, cavity balance, and tensile elongation were significantly superior to that of PPS D2-4.

In particular, PPS D2-1 to D2-3, which additionally contain a heat stabilizer as an additive, have significantly higher tensile strength and tensile elongation than PPS D2-5 which does not contain a heat stabilizer.

Post-processed polyarylene sulfide mixed resin composition

As can be seen in the table above, PPS E1-1 to E1-3 and E1-6 to E1-13 containing the post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin and additives are the first poly It has superior cavity balance, tensile strength, tensile elongation and airtightness compared to PPS A1-1 containing arylene sulfide resin and additives, and outgas amount and cavity balance compared to PPS B1 containing the second polyarylene sulfide resin and additives and excellent tensile elongation, and superior cavity balance and tensile elongation compared to PPS D1-2 including the first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives.

However, PPS E1-7 to E1-13 containing an elastomer as an additive had somewhat lower tensile strength than PPS E1-1 to PPS E1-6, but still higher than PPS A1-1, and PPS A1-1 , the tensile elongation was significantly higher than that of PPS B1 and PPS D1-2.

Moreover, in PPS E1-1 to E1-3 and E1-6 to E1-13, the content of the second polyarylene sulfide resin is based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It was confirmed that the outgas amount, cavity balance, and tensile elongation were excellent even compared to PPS E1-4 and E1-5, which were more than 30% by weight.

As can be seen from the above table, PPS E2-1 to E2-3 containing the post-processed first polyarylene sulfide resin, second polyarylene sulfide resin and additives include the first polyarylene sulfide resin and additives It has superior cavity balance, tensile strength, tensile elongation and airtightness compared to PPS A2, and has excellent outgas volume, cavity balance, tensile strength and tensile elongation compared to PPS B2 containing the second polyarylene sulfide resin and additives, It was confirmed that the cavity balance and tensile elongation were excellent compared to PPS D2-2 including the first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives.

Moreover, PPS E2-1 to E2-3 are PPS E2- in which the content of the second polyarylene sulfide resin is greater than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It was confirmed that the outgas amount, cavity balance, tensile strength and tensile elongation were superior compared to 4 as well.

Claims (17)

a first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; and
A resin composition for a gasket comprising at least one additive selected from the group consisting of glass fibers, elastomers and heat stabilizers.
The method of claim 1,
The additive comprises the glass fiber, or comprises the elastomer and the heat stabilizer, the resin composition for a gasket.
The method of claim 1,
The amount of outgas of the post-processed first polyarylene sulfide resin is 0.001 to 0.20% by weight, or
The disulfide bond fraction of the post-processed first polyarylene sulfide resin is 0.1 to 2.0 wt%, the resin composition for a gasket.
The method of claim 1,
The compatibilizer includes at least one functional group selected from the group consisting of a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.
The method of claim 1,
The compatibilizer is a compound represented by one of the following Chemical Formulas 4 to 6, a resin composition for a gasket:
[Formula 4]

In the above formula,
Y ¹ and Y ² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ ,
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 alkyl group having 1 to 3 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 substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms,
p ¹ and p ² are each independently an integer of 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 may 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 may be connected to each other to form a benzene ring,
The substituted alkyl group of 1 or 2 carbon atoms or the substituted alkenyl group of 1 or 2 carbon atoms of ^{Z 1 '} to Z ^{4' has a substituent of an alkyl group or phenyl group of 1 or 2 carbon atoms,}
The ^{substituted alkyl group or substituted phenyl group having 1 to 3 carbon atoms of B 1} to B ^{7 has} a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms,
provided 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 ;}
[Formula 5]

In the above formula,
Y ^{3 To} Y ⁶ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ ,
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,
R ¹ ' to R ⁴ ' are each independently selected from the group consisting of an alkylene group and an alkoxy group having 1 to 5 carbon atoms,
provided that at least one of ^{Y 3} to Y ^{6 is —SB 9 in} which ^{B 9} is a hydrogen group;
[Formula 6]

In the above formula,
Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ ,
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,
R ⁵ ′ and R ⁶ ′ are each independently an alkylene group having 1 to 5 carbon atoms.
The method of claim 1,
The first polyarylene sulfide resin is post-processed using the compatibilizer at a temperature of 280 to 330 ℃, a resin composition for a gasket.
a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor;
a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and
at least one additive selected from the group consisting of glass fibers, elastomers and heat stabilizers;
The second polyarylene sulfide resin is included 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.
8. The method of claim 7,
The polyarylene sulfide mixed resin composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin has an outgas amount of 0.01 to 1.40% by weight and a disulfide bond fraction of 0.1 to 2.0% by weight, a resin for a gasket composition.
8. The method of claim 7,
A resin composition for a gasket, wherein the first polyarylene sulfide resin and the second polyarylene sulfide resin are melt-mixed at 280 to 330°C.
8. The method of claim 7,
Based on the total weight of the resin composition,
1 to 89% by weight of the first polyarylene sulfide resin,
1 to 38% by weight of the second polyarylene sulfide resin,
A resin composition for a gasket comprising the glass fiber in an amount of 10 to 70% by weight.
8. The method of claim 7,
Based on the total weight of the resin composition,
1 to 98% by weight of the first polyarylene sulfide resin,
1 to 42% by weight of the second polyarylene sulfide resin,
Containing the elastomer in an amount of 0.1 to 20% by weight,
A resin composition for a gasket comprising the heat stabilizer in an amount of 0.01 to 5% by weight.
a post-processed first polyarylene sulfide resin in which an end group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized;
a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and
at least one additive selected from the group consisting of glass fibers, elastomers and heat stabilizers;
The second polyarylene sulfide resin is included in an amount of 0.0001 to 30% by weight based on the total weight of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin.
13. The method of claim 12,
The post-processed polyarylene sulfide mixed resin composed of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin has an outgas amount of 0.01 to 1.40% by weight and a disulfide bond fraction of 0.1 to 2.0% by weight. , a resin composition for a gasket.
13. The method of claim 12,
Based on the total weight of the resin composition,
1 to 89% by weight of the post-processed first polyarylene sulfide resin,
1 to 38% by weight of the second polyarylene sulfide resin,
A resin composition for a gasket comprising the glass fiber in an amount of 10 to 70% by weight.
13. The method of claim 12,
Based on the total weight of the resin composition,
1 to 98% by weight of the post-processed first polyarylene sulfide resin,
1 to 42% by weight of the second polyarylene sulfide resin,
Containing the elastomer in an amount of 0.1 to 20% by weight,
A resin composition for a gasket comprising the heat stabilizer in an amount of 0.01 to 5% by weight.
A gasket for a secondary battery comprising a molded article molded with the resin composition according to any one of claims 1 to 15.
an exterior body having an opening;
a sealing body sealing the opening of the exterior body;
a positive electrode plate, a negative electrode plate, and an electrolyte provided inside the exterior body;
a separator provided between the positive electrode plate and the negative electrode plate;
a positive electrode terminal electrically connected to the positive electrode plate;
a negative terminal electrically connected to the negative electrode plate;
A secondary battery comprising the gasket for a secondary battery according to claim 16 in contact with the positive terminal or the negative terminal.