JP6558030B2 - Polyarylene sulfide resin composition and sealing member for secondary battery sealing plate comprising the same - Google Patents

Description

  The present invention relates to a polyarylene sulfide resin composition, and in particular, since it has excellent bondability to metals in a normal temperature and normal humidity and long-term high temperature and high humidity environment, it is particularly a seal for a secondary battery sealing plate. The present invention relates to a polyarylene sulfide resin composition suitable for a member.

  In recent years, lithium ion batteries have attracted attention as secondary batteries with high voltage and high energy density for in-vehicle use or consumer use.

  Lithium ion batteries need to maintain a sealing property between the inside and outside of the battery container in order to prevent deterioration of the battery. As a seal between the lid plate of the lithium ion battery sealing plate and the electrode terminal, a seal using an O-ring or a seal in which a resin is integrated with a surface-treated metal has been used.

  Polyarylene sulfides (hereinafter sometimes abbreviated as PAS) represented by poly (p-phenylene sulfide) (hereinafter also abbreviated as PPS) have excellent mechanical properties, thermal properties, It has electrical characteristics, is widely used in automotive equipment members, electrical / electronic equipment members, OA equipment members, etc., and is also being studied as a sealing member for lithium-ion batteries. A sealing plate using the contained polyphenylene sulfide resin composition (see, for example, Patent Document 1), a sealing plate using a non-reinforced polyphenylene sulfide resin having a high crystallinity (see, for example, Patent Document 2), and the like have been proposed. ing.

  Moreover, as a polyphenylene sulfide resin composition, a polyarylene sulfide resin composition in which specific alumina is blended with PPS, a secondary battery sealing plate sealing member (see, for example, Patent Document 3) and the like, and the like have been proposed. .

  Further, an olefin polymer containing a glycidyl ester, an acidified polyphenylene sulfide, an elastic body, and a composition containing a metal deactivator depending on the case (see, for example, Patent Document 4), a rare earth element and a transition metal And rare earth transition metal alloy powders, polyphenylene sulfide resins, and injection molding compositions containing heavy metal deactivators (see, for example, Patent Document 5).

Japanese Patent Laying-Open No. 2008-27823 (see, for example, the claims) Japanese Patent Laying-Open No. 2008-27849 (for example, refer to the claims) JP 2012-131896 A (see, for example, the claims). Japanese translation of PCT publication No. 2007-502894 (see, for example, claims) Japanese Patent No. 4821768 (see, for example, the claims).

  However, in the sealing plate proposed in Patent Document 1, since the shrinkage rate of the polyphenylene sulfide resin composition constituting the sealing plate is large and the dimensional accuracy is inferior, there is a problem in reliability as the sealing plate. there were. Moreover, in the sealing board disclosed by patent document 2, the polyphenylene sulfide resin which comprises this sealing board had the subject that it was inferior to the stable productivity for obtaining a good product with a narrow molding condition width | variety. Furthermore, the polyarylene sulfide resin composition proposed in Patent Document 3 has features such as excellent chemical resistance, cold and heat resistance, and good moldability, but has a problem in bonding strength with metals in a long-term high-temperature and high-humidity environment. Remained.

  Further, regarding the composition proposed in Patent Document 4 and the composition for injection molding proposed in Patent Document 5, there are no proposals for applications such as sealing by joining with metal or sealing plates for lithium ion secondary batteries. It is not.

  Therefore, it has been desired to develop a resin excellent in bondability with a metal that can be applied as a sealing member for a secondary battery sealing plate.

  As a result of intensive studies on the above problems, the present inventors have found that a resin composition comprising a specific polyarylene sulfide resin, a specific ethylene copolymer, a metal deactivator and a fibrous filler is used at ordinary temperature. It has been found that it is particularly suitable for a sealing member for a secondary battery sealing plate because it has excellent bonding properties with metal in a humid, long-term, high-temperature and high-humidity environment, and the present invention has been completed.

  That is, the present invention is a polyarylene sulfide having a melt viscosity of 100 to 1000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. A) At least ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b2) with respect to 100 parts by weight , Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer ( 10 to 50 parts by weight of at least one ethylene copolymer (B) selected from the group consisting of b4), a metal deactivator ( ) 0.05 to 2 parts by weight, it relates to a polyarylene sulfide resin composition which comprises a fibrous filler (D) 10 to 80 parts by weight.

  The present invention is described in detail below.

  The polyarylene sulfide (A) constituting the polyarylene sulfide resin composition of the present invention is a high-flow type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg. Polyarylene sulfide having a measured melt viscosity of 100 to 1000 poise. Examples of the polyarylene sulfide (A) include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Examples of the PAS include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, and the like. From the viewpoint of excellent properties and strength characteristics, poly (p-phenylene sulfide) is preferable.

  The PAS (A) is a PAS having a melt viscosity of 100 to 1000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. In particular, since it becomes a PAS resin composition excellent in mechanical strength and thin-wall fluidity, it is preferably 200 to 600 poise PAS. Here, when the melt viscosity is less than 100 poise, a decrease in the mechanical strength of the resin composition is observed. On the other hand, when the melt viscosity exceeds 1000 poise, the resin composition is inferior in thin-wall fluidity, and it has a bonding property with a metal in a normal temperature normal humidity and long-term high temperature high humidity environment when used as a sealing member for a secondary battery sealing plate. It becomes inferior to.

  The PAS (A) can be produced by a method known as a PAS production method, for example, by polymerizing an alkali metal sulfide or a polyhaloaromatic compound in a polar solvent. Is possible. Examples of the polar organic solvent include N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, dimethylformamide, and dimethylacetamide. Examples of alkali metal sulfides include sodium sulfide, rubidium sulfide, and lithium sulfide. Mention may be made of anhydrides or hydrates. Moreover, as an alkali metal sulfide metal salt, you may react the alkali metal hydrosulfide salt and the alkali metal hydroxide. Examples of the polyhaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4′-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobiphenyl and the like can be mentioned.

  Further, as PAS (A), even if it is a linear one, a small amount of polyhalogen compound of trihalogen or higher is added at the time of polymerization to introduce a slight cross-linked or branched structure, Even if the molecular chain is partially and / or terminally modified with a functional group such as a carboxyl group, a carboxy metal salt, an alkyl group, an alkoxy group, an amino group, or a nitro group, it is non-oxidizing such as nitrogen. The heat treatment may be performed in the above inert gas, or a mixture of these structures may be used. In addition, the PAS reduces impurities such as ions and oligomers by performing deionization treatment (acid washing, hot water washing, etc.) before or after heat curing, or washing treatment with an organic solvent such as acetone or methyl alcohol. It may be a thing. Further, it may be cured by heat treatment in an inert gas or an oxidizing gas after completion of the polymerization reaction.

  The ethylene-based copolymer (B) constituting the polyarylene sulfide resin composition of the present invention improves the bondability with the metal of the polyarylene sulfide resin composition, and is an ethylene-α, β-unsaturated carboxylic acid. Acid alkyl ester-maleic anhydride copolymer (b1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer The compound (b3) is at least one selected from the group consisting of ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b4).

  As the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b1), any copolymer may be used as long as it belongs to this category. Among them, the polyarylene sulfide resin composition obtained can be used. Since the product is excellent in bondability with metal and the like, ethylene residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) = 50 to 98:40 to 1 : It is preferable that it is the range of 10-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b1) include (trade name) Bondine LX4110 (manufactured by Arkema), (trade name) Bondine TX8030 (Arkema). (Trade name) Bondine AX8390 (manufactured by Arkema) and the like.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b2), any copolymer belonging to this category may be used. Among them, the polyarylene sulfide resin composition obtained is a metal and Therefore, it is preferable that ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) = 85 to 99:15 to 1 in range. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b2) include (trade name) Bond First 2C (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) Bond First E ( Sumitomo Chemical Co., Ltd.).

  Any ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b3) may be used as long as it belongs to this category, and polyarylene sulfide resin composition obtained among them may be used. Is excellent in bonding properties with metals, etc., ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: vinyl acetate residue unit (weight ratio) = 50 to 98:15 to 1:35 A range of ˜1 is preferable. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b3) include (trade name) Bond First 2B (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) bond. First 7B (Sumitomo Chemical Co., Ltd.) etc. are mentioned.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b4), any copolymer belonging to this category may be used. Since the resulting polyarylene sulfide resin composition is excellent in heat resistance and the like, ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit ( The weight ratio is preferably in the range of 50 to 98:10 to 1:40 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b4) include (trade name) Bond First 7L (Sumitomo Chemical Co., Ltd.) Manufactured), (trade name) Bond First 7M (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  The α-olefin constituting the ethylene copolymer (B) means an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1, hexene-1, Examples include octene-1 and the like. Examples of the α, β-unsaturated carboxylic acid alkyl ester include alkyl esters such as acrylic acid and methacrylic acid, and specifically include methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. Isopropyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylic acid t- Examples include butyl. Examples of the α, β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

  The blending amount of the ethylene copolymer (B) constituting the polyarylene sulfide resin composition of the present invention is 10 to 50 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the ethylene copolymer (B) is less than 10 parts by weight, the resulting composition is inferior in bondability with a metal. On the other hand, when the blending amount of the ethylene-based copolymer exceeds 50 parts by weight, the resulting composition is inferior to mold fouling and molded product appearance, and has a large amount of gas generated during molding.

  Any metal deactivator (C) constituting the polyarylene sulfide resin composition of the present invention may be used as long as it belongs to a category called a metal deactivator. N'-diphenyloxamide, 2,4-dicaproyl resorciferone, 2-thiobarbituric acid, N, N'-bis (o-mercaptophenyl) thiourea, N-salicylidene-N'-salicylhydrazide , M-nitrobenzhydrazide, diacetyldisalicylhydrazone, 3-aminophthalhydrazide, phthalic acid dihydrazide, mercaptoacetylaminotriazole, adipic acid hydrazide, N- (2,5-dihydroxybenzoyl) phenylhydrazine, N′-benzoylpyrrolidonecarboxylic acid Acid hydrazide, 2-hydroxyacetophenone hydrazone Salicylaldehyde oxalyl dihydrazone, 8-oxyquinoline, N-acetyl-N′-salicyloyl hydrazine, di-o-hydroxyanilide tartaric acid, rubean hydrogen acid, oxalobis (2-hydroxy-5-octylbenzylidene hydrazide), apple Acid, azimidobenzene, thiodipropionylaminotriazole, 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide, N′1, N′12-bis (2-hydroxybenzoyl) dodecanedihydrazide N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and the like, and tris (2-tert-butyl-5-methyl-4) -Thio-5'-tert-butyl-4'-hydroxy-2-methyl Phenyl) phenyl phosphite, 1,2-bis (3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl) hydrazine, N, N′-bis (2- (2- (3,5 -Di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy) ethyl) oxamide and the like, and in particular, since it becomes a polyarylene sulfide resin composition excellent in bondability with metal, 2-hydroxy-N- 1H-1,2,4-triazol-3-ylbenzamide, N′1, N′12-bis (2-hydroxybenzoyl) dodecanedihydrazide, N, N′-bis (3- (3,5-di-tert -At least one metal deactivator selected from the group consisting of -butyl-4-hydroxyphenyl) propionyl) hydrazine Preferably, tris (2-tert-butyl-5-methyl-4-thio-5′-tert-butyl-4′-hydroxy-2-methylphenyl) phenyl phosphite, 1,2-bis (3- ( 4-hydroxy-3,5-di-tert-butylphenyl) propionyl) hydrazine, N, N′-bis (2- (2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy) It is preferably at least one metal deactivator selected from the group consisting of :) ethyl) oxamide.

  The compounding quantity of this metal deactivator (C) which comprises the polyarylene sulfide resin composition of this invention is 0.05-2 weight part with respect to 100 weight part of polyarylene sulfide (A). When the compounding quantity of this metal deactivator (C) is less than 0.05 weight part, the composition obtained will be inferior to bondability with a metal. On the other hand, when the compounding amount of the metal deactivator (C) exceeds 2 parts by weight, the effect of improving the bonding property commensurate with the compounding amount cannot be obtained, and the amount of gas generated during molding is large. . And since the composition obtained especially becomes what becomes excellent in joining property with a metal, it is preferable that it is 0.2-2 weight part with respect to 100 weight part of polyarylene sulfide (A).

  The fibrous filler (D) constituting the polyarylene sulfide resin composition of the present invention is blended in order to improve the mechanical strength and dimensional stability of the polyarylene sulfide resin composition. Any fibrous filler can be used as long as it can achieve the above. Examples of the fibrous filler (D) include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, stone koji fiber, and metal fiber. Among them, glass fiber is preferable. Since the fibrous filler (D) has a high mechanical strength of the polyarylene sulfide resin composition, the surface of the fibrous filler (D) is an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like. It is preferable that it has been processed.

  The compounding quantity of this fibrous filler (D) which comprises the polyarylene sulfide resin composition of this invention is 10-80 weight part with respect to 100 weight part of polyarylene sulfide (A). When the compounding quantity of this fibrous filler (D) is less than 10 weight part, the composition obtained will be inferior to mechanical strength. On the other hand, when the blending amount of the fibrous filler (D) exceeds 80 parts by weight, the resulting composition is inferior in toughness, melt flowability, and molded product appearance.

  The polyarylene sulfide resin composition of the present invention may contain a non-fibrous filler without departing from the object of the present invention. Examples of the non-fibrous filler include wollastonite, zeolite, and sericite. Silicates such as sites, kaolin, clay, pyrophyllite, bentonite, alumina silicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, iron oxide; magnesium carbonate, dolomite, etc. Examples thereof include carbonates; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride and aluminum nitride; glass beads; magnesium hydroxide and the like. Among them, clay magnesium hydroxide and glass beads are preferable. The non-fibrous filler may be a surface treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like.

  Furthermore, the polyarylene sulfide resin composition of the present invention is within a range not departing from the object of the present invention, various thermosetting resins, thermoplastic resins such as epoxy resins, cyanate ester resins, phenol resins, polyimides, silicone resins, One or more of polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone and the like can be mixed and used.

  The production method for producing the PAS resin composition of the present invention is not particularly limited, and a method known as a general mixing / kneading method can be used. For example, all raw materials are blended. Melt-kneading method; Melting and kneading after mixing a part of raw materials, and further mixing and melting and kneading the remaining raw materials; or mixing a part of raw materials after mixing with a single or twin screw extruder Any method may be used such as a method of mixing the remaining raw materials using a side feeder. Moreover, about a small amount of addition component, after kneading | mixing and pelletizing another component by said method etc., you may use it by adding before shaping | molding. As a method for performing melt kneading, a conventionally used heat melt kneading method can be used, for example, a heat melt kneading method using a single or twin screw extruder, a kneader, a mill, a Brabender, or the like. In particular, a melt-kneading method using a twin screw extruder excellent in kneading ability is preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 270-350 degreeC.

  The polyarylene sulfide resin composition of the present invention is excellent in bondability with a metal and can be applied to various applications, and among them, it is easy from a sealing member for a secondary battery sealing plate, particularly an electrolyte. Sealing member disposed between the electrode terminal and the cover plate whose surface is roughened by physical roughening treatment and / or chemical roughening treatment of a lithium ion battery sealing plate that easily generates hydrofluoric acid Preferably, it can be suitably used as a seal member disposed between an electrode terminal whose surface is roughened by physical roughening treatment and / or anodizing treatment and the lid plate.

  Here, the secondary battery sealing plate is a member of a secondary battery container including an electrode terminal, a cover plate, and an insulating seal member, and a schematic diagram is shown in FIG. Here, 1 and 2 indicate electrode terminals whose surfaces are roughened by physical roughening treatment and / or chemical roughening treatment, etc., preferably by physical roughening treatment and / or anodizing treatment, It is preferably composed of a pair of metals for the positive electrode and the negative electrode, and is at least one metal selected from aluminum, an aluminum alloy, copper, and a copper alloy. 3 shows a sealing member, and the sealing member is preferably made of the PAS resin composition of the present invention. 4 represents a cover plate whose surface is roughened by physical roughening treatment and / or chemical roughening treatment, preferably physical roughening treatment and / or anodizing treatment, etc. Mention may be made of metals such as aluminum, iron and stainless steel.

  And since the electrode terminal and the lid plate are excellent in sealing properties between the electrode terminal and the lid plate and the sealing member, particularly the sealing member made of the polyarylene sulfide resin composition of the present invention, Electrode terminals and cover plates whose surfaces are roughened by physical roughening and / or chemical roughening, etc., preferably by physical roughening and / or anodizing.

  Examples of the chemical roughening treatment include an anodizing treatment method, a chemical treatment method using an acid or alkali aqueous solution, and the like.

  The chemical treatment with an acid or alkali aqueous solution may be, for example, a method in which a metal member such as an electrode terminal or a cover plate is immersed in an acid or alkali aqueous solution to chemically treat the surface of the metal member. Examples of the acid or alkali aqueous solution include phosphoric acid compounds such as phosphoric acid; chromic acid compounds such as chromic acid; hydrofluoric acid compounds such as hydrofluoric acid; nitric acid compounds such as nitric acid; A hydrochloric acid compound of sulfuric acid; a sulfuric acid compound such as sulfuric acid; an aqueous alkali solution such as sodium hydroxide and an aqueous ammonia solution; a method of chemical treatment with an aqueous triazine thiol solution and an aqueous triazine thiol derivative; JP-A-10-096088, JP-A-10-056263, JP-A-4-035855, JP-A-4-032. 83, JP-A No. 02-298284, JP-WO2009 / 151 099 discloses include a method proposed such as Japanese Patent WO2011 / 104,944, and the like.

  As an anodic oxidation method, a metal member such as an electrode terminal and a cover plate is used as an anode to perform an electrification reaction in an electrolytic solution to form an oxide film on the surface thereof. For example, 1) a DC electrolysis method in which electrolysis is performed by applying a constant DC voltage, and 2) a bipolar electrolysis method in which electrolysis is performed by applying a voltage in which an AC component is superimposed on a DC component. , Etc. Furthermore, as a physical surface roughening method, there is a method of roughening the surface by physical means such as contacting or colliding fine solid particles with a metal surface or irradiating with high energy electromagnetic radiation, for example, sandblasting And a method known as liquid honing treatment. Examples of the abrasive used in the sand blasting process and the liquid honing process include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, and plastic beads.

  The PAS resin composition of the present invention comprises the electrode terminal and the cover plate whose surfaces are roughened by physical roughening treatment and / or chemical roughening treatment, preferably physical roughening treatment and / or anodizing treatment. By fixing an object as a seal member, the electrode terminal, the cover plate, and the PAS resin composition have excellent bondability in a normal temperature normal humidity and long-term high temperature and high humidity environment. When fixing as a sealing member, a method of caulking the electrode terminal and the cover plate with the sealing member, a method of performing integral molding for fixing the electrode and the cover plate, and the like can be mentioned. Among them, since the method is particularly excellent in productivity, the present invention can be applied to the electrode terminal and / or the cover plate by metal insert molding using, for example, an injection molding machine, an extrusion molding machine, a compression molding machine or the like. The PAS resin composition is molded as a sealing member and integrated.

  Since the polyarylene sulfide resin composition of the present invention has excellent bondability with metals in a normal temperature and normal humidity and long-term high temperature and high humidity environment, in particular, a sealing member for a secondary battery sealing plate, a lithium ion battery sealing plate It has excellent characteristics as a sealing member.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  The polyarylene sulfide (A), the ethylene copolymer (B), the metal deactivator (C), and the fibrous filler (D) used in the examples and comparative examples are shown below.

<Polyarylene sulfide (A)>
Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a1-2)): Melt viscosity 400 poise.
Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a1-3)): Melt viscosity 1600 poise.
Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a2-1)): Melt viscosity 450 poise.

<Ethylene copolymer (B)>
Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b1-1) (hereinafter simply referred to as ethylene copolymer (b1-1)): manufactured by Arkema Co., Ltd. Product Name) Bondine AX8390.
Ethylene-α, β-unsaturated carboxylic acid-glycidyl ester copolymer (b2-1) (hereinafter simply referred to as ethylene copolymer (b2-1)): manufactured by Sumitomo Chemical Co., Ltd. (trade name) ) Bond First E.
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b3-1) (hereinafter simply referred to as ethylene copolymer (b3-1)): manufactured by Sumitomo Chemical Co., Ltd. ( Product name) Bond First 7B.
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-alkyl ester copolymer (b4-1) (hereinafter simply referred to as ethylene copolymer (b4-1)): manufactured by Sumitomo Chemical Co., Ltd. ( Product name) Bond First 7M.

<Metal deactivator (C)>
2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide (c-1) (hereinafter simply referred to as metal deactivator (c-1)): manufactured by ADEKA Corporation, (Product Name) ADK STAB CDA-1.
N′1, N′12-bis (2-hydroxybenzoyl) dodecanedihydrazide (c-2) (hereinafter simply referred to as metal deactivator (c-2)): manufactured by ADEKA Corporation (trade name) ) Adeka Stub CDA-6.
N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine (c-3) (hereinafter simply referred to as metal deactivator (c-3)). ): Manufactured by ADEKA Corporation, (trade name) ADK STAB CDA-10.
Tris (2-tert-butyl-5-methyl-4-thio-5′-tert-butyl-4′-hydroxy-2-methylphenyl) phenyl phosphite (c-4) (hereinafter simply referred to as a metal deactivator ( c-4)): manufactured by Clariant, (trade name) Hostanox OSP1.
1,2-bis (3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl) hydrazine (c-5) (hereinafter simply referred to as metal deactivator (c-5)): (Product name) Irganox MD1024, manufactured by BASF.
N, N′-bis (2- (2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy) ethyl) oxamide (c-6) (hereinafter simply referred to as metal deactivator (c -6).): (Product name) Nowguard XL-1 manufactured by Advant.

<Fibrous filler (D)>
Glass fiber (d-1); manufactured by Nippon Electric Glass Co., Ltd. (trade name) T-760H.

<Synthesis Example 1 (Synthesis of PPS (a1-2))>
A 50 liter autoclave equipped with a stirrer was charged with 6214 g of sodium sulfide 2.9 hydrate and 17000 g of N-methyl-2-pyrrolidone, gradually heated to 205 ° C. while stirring under a nitrogen stream, and 1355 g of water was added. Distilled off. After cooling the system to 140 ° C., 7150 g of p-dichlorobenzene, 47 g of 3,5-dichloroaniline (about 0.6 mol% based on the total amount of p-dichlorobenzene and 3,5-dichloroaniline), N— 5000 g of methyl-2-pyrrolidone was added and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours. After the polymerization, the mixture was cooled to room temperature and the solid content was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried at 100 ° C. for a whole day and night, whereby amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (a1-1)) having a melt viscosity of 250 poise was obtained. Obtained. This PPS (a1-1) was further cured at 250 ° C. for 4 hours under a nitrogen atmosphere to obtain amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (a1-2)).

  The obtained PPS (a1-2) had a melt viscosity of 400 poise.

  Further, the obtained PPS (a1-2) was cured in an oxygen atmosphere at 230 ° C. for 4 hours to obtain amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (a1-3) having a melt viscosity of 1600 poise. I wrote.)

<Synthesis Example 2 (Synthesis of PPS (a2-1))>
A 50 liter autoclave equipped with a stirrer was charged with 5607 g of a 47% aqueous solution of sodium hydrogen sulfide, 3807 g of a 48% aqueous solution of sodium hydroxide and 10773 g of N-methyl-2-pyrrolidone, and gradually heated to 200 ° C. with stirring under a nitrogen stream. 4533 g of water was distilled off. After cooling the system to 170 ° C., 7060 g of p-dichlorobenzene and 5943 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C, polymerized at 225 ° C for 1 hour, further heated to 250 ° C, and polymerized at 250 ° C for 2 hours. Further, 1503 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was carried out at 225 ° C. for 3 hours. After the polymerization, the mixture was cooled to room temperature and the solid content was isolated using a centrifuge. The solid content was washed with N-methyl-2-pyrrolidone at 130 ° C., then repeatedly washed with warm water, and dried at 100 ° C. overnight, so that a linear poly (p-phenylene sulfide) having a melt viscosity of 450 poise was obtained. (Hereinafter referred to as PPS (a2-1))).

  Evaluation and measurement methods of the polyarylene sulfide obtained by the synthesis example and the polyarylene sulfide resin composition obtained by the examples are shown below.

~ Measurement of melt viscosity of PAS ~
Measurement of melt viscosity under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka type flow tester (manufactured by Shimadzu Corporation, (trade name) CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm. Went.

-Bondability of PAS resin composition and copper plate at 23 ° C-
A copper (C1100) flat plate having a length of 45 mm, a width of 18 mm, and a thickness of 1.5 mm is degreased with acetone and then subjected to a liquid honing treatment with # 600 alumina and then # 2000 alumina to roughen the surface. A flat plate was obtained. Then, the copper flat plate was fitted into an injection mold, and the PAS resin composition was insert-molded using an injection molding machine. By performing insert molding under the conditions of a cylinder temperature of 310 ° C., a cooling time of 40 seconds, and a mold temperature of 135 ° C., a shear tensile test piece in which the PAS resin composition and a copper plate were integrated was produced. The bonding surface between the PAS resin composition and the copper plate was 10 mm in the width direction of the copper plate and 5 mm in the length direction. Next, the tensile strength at break, that is, the joint strength of the joint surface was measured using the shear tensile test piece. Using a measuring device (manufactured by Shimadzu Corp., (trade name) AG-5000B), a shear tensile test was performed under the conditions of a distance between chucks of 55 mm and a tensile speed of 10 mm / min in an environment of 23 ° C. and 50% Rh. Those having a bonding strength of 40 MPa or more were judged to be excellent in bondability at room temperature.

-Bondability of PAS resin composition and copper plate under high temperature and high humidity environment-
The shear tensile test piece was left in the constant temperature and humidity chamber for 1000 hours in a state where the constant temperature and humidity chamber was maintained at 85 ° C. and 85% Rh. Next, the shear tensile test piece taken out from the constant temperature and humidity chamber was allowed to stand in an environment of 23 ° C. and 50% Rh for 24 hours, and then the joint strength of the joint surface was measured. Using a measuring apparatus (manufactured by Shimadzu Corporation, (trade name) AG-5000B), a shear tensile test was performed under the conditions of 23 ° C. and 50% Rh, with a distance between chucks of 55 mm and a measurement speed of 10 mm / min. With respect to the bonding strength at room temperature, a material having a retention rate of 80% or more after being left in the constant temperature and humidity chamber for 1000 hours was judged to be excellent in bonding property in a high temperature and high humidity environment.

~ Generated gas ~
When insert molding of the polyarylene sulfide resin composition using an injection molding machine, the gas generated from the tip of the nozzle of the molding machine is hardly recognized as ◯, and the gas with a lot of gas is determined as X. did. It was judged that the generated gas was excellent when the generated gas was ○.

~ Mold contamination ~
100 pieces of the shear tensile test pieces were continuously formed by injection molding, and then the presence or absence of contaminants adhering in the mold cavity was observed. The case where no contaminant was found was judged as ◯, and the case where even a slight amount of contaminant was found was judged as ×. The mold contamination property was judged to be excellent when there was no mold contamination.

-Preparation of secondary battery sealing plate-
The aluminum (A1050) lid plate having the shape shown in FIG. 2 and the aluminum (A1050) flat plate having the shape shown in FIG. 3 are degreased with acetone and then immersed in a 1% aqueous sodium hydroxide solution and then a 10% aqueous sulfuric acid solution. An anodizing treatment was performed in a 15% sulfuric acid aqueous solution at a current density of 0.5 A / cm ³ to obtain an aluminum lid plate and an aluminum electrode terminal having a roughened surface.

  Also, a copper (C1100) flat plate having the shape shown in FIG. 3 is prepared, and after degreasing with acetone, a liquid honing process is performed with # 600 alumina and then # 2000 alumina to roughen the surface. Got.

  The PAS resin composition is insert-molded with an injection molding machine so as to have the shape shown in FIG. 1 for each of the aluminum lid plate, the aluminum electrode and the copper electrode whose surfaces are roughened, and the secondary battery. A sealing plate was produced.

-Bondability of secondary battery sealing plate sealing material under high temperature and high humidity environment-
The secondary battery sealing plate was left in the constant temperature and humidity chamber for 1000 hours in a state where the constant temperature and humidity chamber was maintained at 85 ° C. and 85% Rh. Next, the secondary battery sealing plate taken out from the constant temperature and humidity chamber is allowed to stand for 24 hours in an environment of 23 ° C. and 50% Rh, and then the electrode terminal and the lid plate are sealed with the PAS resin composition. Red ink was applied to the areas. Next, the secondary battery sealing plate is left in a sealable desiccator, and the air in the desiccator is sucked in until the atmospheric pressure in the desiccator reaches 0.1 kPa, and after 1 hour, the atmospheric pressure in the desiccator Released. Thereafter, the red ink of the secondary battery sealing plate taken out from the desiccator was washed, and a developer for inspection was further applied to visually observe the sealing property. A case where no red ink oozes out from the seal portion was recognized was evaluated as ◯, and a case where even a slight oozing out was observed was determined as x. Regarding the bondability of the sealing member for a secondary battery sealing plate in a high-temperature and high-humidity environment, it was judged that the bondability was excellent when it was “◯”.

Example 1
PPS (a1-2) 62.9% by weight, ethylene copolymer (b1-1) 15.1% by weight, metal deactivator (c-1) 1.9% by weight, It put into the hopper of the twin-screw extruder (Toshiba machine make, (brand name) TEM-35-102B) heated to the cylinder temperature of 310 degreeC. On the other hand, the glass fiber (d-1) is put into the hopper of the side feeder of the twin-screw extruder, melted and kneaded at a screw rotation speed of 200 rpm, and the molten composition flowing out from the die is cooled and cut into pellets. A polyarylene sulfide resin composition was prepared. In this case, the polyarylene sulfide resin composition was composed of 23 parts by weight of an ethylene copolymer (b1-1), 100 parts by weight of PPS (a1-2), and a metal deactivator (c-1). The amount was 0.8 part by weight and 31 parts by weight of glass fiber (d-1).

  Using the polyarylene sulfide resin composition, the bondability of the PAS resin composition and the copper plate at 23 ° C., the bondability of the PAS resin composition and the copper plate in a high-temperature and high-humidity environment, generated gas, mold contamination Was evaluated. Furthermore, the secondary battery sealing board using this PAS resin composition was produced, and the joining property in the high temperature, high humidity environment of this sealing member for secondary battery sealing boards was evaluated. These results are shown in Table 1.

  The resulting polyarylene sulfide resin composition was excellent in bondability at 23 ° C. and in a high-temperature and high-humidity environment, and excellent in mold contamination and generated gas during molding. Moreover, the obtained sealing member for a secondary battery sealing plate was excellent in bondability in a high temperature and high humidity environment.

Examples 2-10
PPS (a1-2, a2-1), ethylene copolymer (b1-1, b2-1, b3-1, b4-1), metal deactivator (c-1, c-2, c- 3) A polyarylene sulfide resin composition and a secondary battery sealing plate were produced in the same manner as in Example 1 except that the blending ratios of glass fiber (d-1) shown in Tables 1 and 2 were changed. Then, the evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

  All the obtained polyarylene sulfide resin compositions were excellent in bondability at 23 ° C. and in a high-temperature and high-humidity environment, and excellent in mold contamination and generated gas during molding. Moreover, all the obtained sealing members for secondary battery sealing plates were excellent in bondability in a high temperature and high humidity environment.

実施例１１〜１５
ＰＰＳ（ａ１−２）、エチレン系共重合体（ｂ１−１、ｂ４−１）、金属不活性化剤（ｃ−４、ｃ−５、ｃ−６）及びガラス繊維（ｄ−１）を表３に示す配合割合となるようにした以外は、実施例１と同様の方法によりポリアリーレンスルフィド樹脂組成物および二次電池封口板を作製し、実施例１と同様の方法により評価した。評価結果を表３に示す。

Examples 11-15
PPS (a1-2), ethylene copolymer (b1-1, b4-1), metal deactivator (c-4, c-5, c-6) and glass fiber (d-1) are represented. A polyarylene sulfide resin composition and a secondary battery sealing plate were produced in the same manner as in Example 1 except that the blending ratio shown in 3 was used, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

  All the obtained polyarylene sulfide resin compositions were excellent in bondability at 23 ° C. and in a high-temperature and high-humidity environment, and excellent in mold contamination and generated gas during molding. Moreover, all the obtained sealing members for secondary battery sealing plates were excellent in bondability in a high temperature and high humidity environment.

比較例１〜７
ＰＰＳ（ａ１−２、ａ１−３）、エチレン系共重合体（ｂ１−１、ｂ４−１）、金属不活性化剤（ｃ−１、ｃ−３）及びガラス繊維（ｄ−１）を表３に示す配合割合となるようにした以外は、実施例１と同様の方法により組成物及び二次電池封口板を作製し、実施例１と同様の方法により評価した。評価結果を表４に示した。

Comparative Examples 1-7
PPS (a1-2, a1-3), ethylene copolymer (b1-1, b4-1), metal deactivator (c-1, c-3) and glass fiber (d-1) are represented. A composition and a secondary battery sealing plate were produced in the same manner as in Example 1 except that the blending ratio shown in 3 was used, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

  The compositions obtained from Comparative Examples 1, 2, 3, and 6 were inferior in bonding strength at 23 ° C. The compositions obtained by Comparative Examples 1, 2, 4, and 6 were inferior in bondability under high temperature and high humidity. The compositions obtained from Comparative Examples 2, 5, and 7 were inferior in mold fouling due to a large amount of gas generated during insert molding using the obtained compositions. Moreover, the sealing member for secondary battery sealing plates produced using the compositions obtained from Comparative Examples 1, 2, 3, 4, 5, 6, and 7 is inferior in bondability under high temperature and high humidity. there were.

  The polyarylene sulfide resin composition of the present invention is excellent in bondability with a metal in a normal temperature and normal humidity and long-term high temperature and high humidity environment, has a small amount of gas generated during molding, and has excellent mold contamination. In particular, it has excellent characteristics as a sealing member for a secondary battery sealing plate and a sealing member for a lithium ion battery sealing plate, and its industrial applicability is extremely high.

; Schematic of a secondary battery sealing plate. ; Schematic showing the cover plate used in Examples and Comparative Examples (unit: mm) Schematic showing the electrodes used in the examples and comparative examples (unit: mm)

1; Aluminum electrode terminal 2; Copper electrode terminal 3; Seal member 4;

Claims (6)

100 parts by weight of polyarylene sulfide (A) having a melt viscosity of 100 to 1000 poise measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. On the other hand, at least ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b2), ethylene-α, β -From the group consisting of unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b4). 10 to 50 parts by weight of at least one ethylene copolymer (B) selected, 0.05 to 2 metal deactivator (C) The amount unit, fibrous filler (D) viewed contains from 10 to 80 parts by weight, metal deactivators (C) is 2-hydroxy -N-1H-1,2,4- triazol-3-yl benzamide, N′1, N′12-bis (2-hydroxybenzoyl) dodecanedihydrazide, N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, tris (2 Tert-butyl-5-methyl-4-thio-5′-tert-butyl-4′-hydroxy-2-methylphenyl) phenyl phosphite, 1,2-bis (3- (4-hydroxy-3,5 -Di-tert-butylphenyl) propionyl) hydrazine, N, N'-bis (2- (2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy) ethyl) A polyarylene sulfide resin composition, wherein the at least one metal deactivator selected from the group consisting of oxamides and the fibrous filler (D) are glass fibers . The polyarylene sulfide resin composition according to claim 1, comprising 0.2 to 2 parts by weight of a metal deactivator (C) with respect to 100 parts by weight of the polyarylene sulfide (A). The polyarylene sulfide resin composition according to claim 1 or 2, which is a polyarylene sulfide resin composition for metal bonding . A sealing member for a secondary battery sealing plate for integrating a metal electrode terminal and a metal lid plate subjected to a surface treatment by physical treatment and / or chemical treatment, and comprising: A sealing member for a secondary battery sealing plate, comprising the polyarylene sulfide resin composition described above. 5. A sealing member for a secondary battery sealing plate for integrating a metal electrode terminal and a metal lid plate subjected to a physical roughening and / or anodizing surface treatment. The sealing member for secondary battery sealing plates of description. The sealing member for a secondary battery sealing plate according to claim 4, wherein the sealing member is a sealing member for a lithium ion battery sealing plate.

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