JP2022036538A - Insulating member for battery made of polyphenylene sulfide resin composition and manufacturing method - Google Patents

Abstract

To provide an insulating member for a battery made of a polyphenylene sulfide resin composition that combines excellent hydrofluoric acid resistance and resistance to clamping.SOLUTION: The insulating member for a battery consists of a polyphenylene sulfide resin composition containing (a) a polyphenylene sulfide resin and (b) an organosilane compound. A test piece (ISO527-2-1A) obtained by injection molding the resin composition has a tensile breaking elongation of 5% or more in a tensile test (ISO527-1,2) after immersion in hydrofluoric acid (50% aqueous solution) for 500 hours under 60°C conditions.SELECTED DRAWING: None

Description

The present invention relates to an insulating member for a battery made of a polyphenylene sulfide resin composition having excellent hydrogen fluoride acid resistance, caulking resistance, toughness of a welded portion, and heat resistance.

The battery is provided with various insulating members for the purpose of preventing an internal short circuit. Polyolefin-based resins such as polyethylene resin and polypropylene resin, which have electrolytic solution resistance and toughness, have been used for conventional insulating members in order to ensure safety during actual use. In recent years, due to the miniaturization of electronic devices and the widespread use of electric vehicles, the capacity and energy density of secondary batteries have been increasing. Therefore, in the secondary battery, the insulating member is exposed to a higher temperature when an abnormality occurs, and the insulating member is also required to have heat resistance. Against this background, the creation of insulating members such as insulating plates made of new resin materials that have toughness, high-temperature rigidity, molding processability, and heat resistance, instead of polyolefin resins such as polyethylene resin and polypropylene resin, has been created. It has been demanded. As an insulating member using a resin other than a polyolefin resin, for example, in Patent Document 1, by using a laminated plate of a phenol resin containing a glass cloth as a base material and an inorganic additive as an insulating plate, heat during overcharging is used. It is described that the curing shrinkage of the phenol resin due to the above can be suppressed, and the deformation of the electrode plate group formed via the positive electrode plate, the negative electrode plate, and the separator can be prevented.

On the other hand, in a lithium ion secondary battery, generally, as described in Patent Document 2, for example, cyclic carbonates such as propylene carbonate and ethylene carbonate and chain carbonates such as dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate are used as non-aqueous electrolytes. A mixed solvent is used, and a fluorine compound such as LiPF6 or LiBF4 is used as the supporting salt. However, when a fluorine compound is used, hydrofluoric acid (HF) is generated by reacting with a trace amount of water in the battery, and the generated HF has a problem of deteriorating peripheral members such as an insulating member. Therefore, for example, Patent Document 3 describes a sealing gasket made of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) having excellent resistance to non-aqueous electrolytes and acid resistance to hydrogen fluoride.

Further, as a method for manufacturing an insulating member for a battery, injection molding having excellent mass productivity is widely used. However, since an insulating member such as an insulating plate has an opening or a through hole for fitting a terminal, an injection molding method is used. In the case of molding by, two or more resin flows are generated in the annular cavity, and a fragile weld line is generated when these resin flows merge with each other. For example, as described in Patent Document 4, it is known that in the process of manufacturing a battery, a so-called "caulking process" of pressing or tightening a joint when fitting an insulating member such as an insulating plate is performed. However, when the insulating member or gasket having the welded portion is crimped, there is a problem that the load causes cracks in the welded portion and does not play a role as the insulating member or the gasket. In addition, the weld portion cannot follow the deformation of the insulating member due to the swelling of the battery due to the increase in internal pressure that occurs when the battery is used, and cracks and breaks occur in the weld portion, which does not play the role of an insulating member or a gasket. There is a risk. On the other hand, Patent Document 4 describes a method for manufacturing a gasket that does not generate a weld line by cutting and flaring a cylinder obtained by extrusion molding.

Further, Patent Document 5 describes a manufacturing process in which a sheet-shaped PFA is punched into a molded product shape and then subjected to hot pressure and cold pressure treatment.

JP-A-2002-231314. Japanese Unexamined Patent Publication No. 8-321326 Japanese Unexamined Patent Publication No. 2006-147159 Japanese Unexamined Patent Publication No. 2007-48882 International Publication No. 2014/129413

However, the material described in Patent Document 1 has a problem that it does not have resistance to hydrofluoric acid. In addition, although welded parts do not occur because it is produced by punching, the base material of glass cloth is impregnated with phenol resin and then heat-cured to form a laminated board, which is further punched to improve productivity. There is a difficulty in terms of perspective.

Patent Documents 3 to 5 all use PFA resin, which is an expensive resin, which is not preferable in terms of cost. Further, the manufacturing method described in Patent Document 4 is more productive than injection molding, although a weld portion does not occur because a tubular molded product is obtained by extrusion molding and then processed into a gasket shape. Not preferable from the viewpoint.

Further, the manufacturing method described in Patent Document 5 is more productive than injection molding, although a weld portion does not occur because a sheet is produced, punched into a molded product, and further subjected to a step of applying hot pressure and cold pressure. Not preferable from the viewpoint.

As a result of studies to solve the above problems, the present inventors have found that (a) a polyphenylene sulfide resin and (b) a polyphenylene sulfide resin composition containing an organic silane compound are superior to hydrofluoric acid. We have found that the insulating member such as an insulating plate using the resin composition has excellent chemical resistance, caulking resistance, toughness of a welded portion, and heat resistance. That is, the present invention has been made to solve at least a part of the above-mentioned problems, and can be implemented as the following embodiments.
(1) An insulating member for a battery, wherein the insulating member comprises (a) a polyphenylene sulfide resin and (b) a polyphenylene sulfide resin composition containing an organic silane compound, and the resin composition is injection-molded. In a tensile test (ISO527-1 and 2) after immersing the test piece (ISO527-2-1A) in hydrofluoric acid (50% aqueous solution) under 60 ° C. conditions for 500 hours, a tensile breakage of 5% or more was obtained. Insulation member for batteries with elongation.
(2) The test piece (ISO527-2-1A) obtained by injection molding the resin composition, which is the insulating member for a battery according to (1), is mixed with hydrofluoric acid (50% aqueous solution) at 60 ° C. A battery insulating member having a weight change rate of 2% or less before and after immersion under conditions of immersion for 500 hours.
(3) The insulating member for a battery according to (1) or (2), which is obtained by injection molding the resin composition and has a thickness of 1.6 mm in which a weld portion is formed in the central portion between marked lines. In a tensile test of a test piece with a width of 6 mm and a distance between marked lines of 50 mm, measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min, the tensile load represented by the area under the curve of the stress-strain curve is 100 MPa ·% or more. Insulation member for batteries.
(4) The thickness 1 of the battery insulating member according to any one of (1) to (3), wherein a weld portion is formed in a central portion between marked lines, which is obtained by injection molding the resin composition. A battery insulating member having a tensile elongation at break of 3.0% or more in a tensile test of a test piece having a width of 1.6 mm, a width of 6 mm, and a distance between marked lines of 50 mm, measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min.
(5) The test piece according to any one of (1) to (4), wherein a weld portion is formed in the central portion between marked lines obtained by injection molding the resin composition. , A battery insulating member having a tensile strength of 45 MPa or more in a tensile test in an atmosphere of 80 ° C.
(6) The insulating member for a battery according to any one of (1) to (5), wherein the resin composition contains 80 wt of (c) an olefin component with respect to 100 parts by weight of (a) PPS resin. % Or more content of the polyolefin monomer or polyolefin copolymer is less than 1 part by weight.
(7) The battery insulating member according to any one of (1) to (6), wherein the resin composition has a melt viscosity (measurement conditions: temperature 320 ° C., shear rate 2432 / s) of 250 Pa. Insulation member for batteries that is s or less.
(8) The insulating member for a battery according to any one of (1) to (7), in terms of polystyrene in the molecular weight distribution obtained from the measurement of gel permeation chromatography (GPC) of the resin composition. The proportion of components detected earlier than the elution time corresponding to the molecular weight of 750000 is 0.4 to 8.5%, and the weight average molecular weight of the components detected later than the elution time corresponding to the polystyrene-equivalent molecular weight of 750000 is Insulation member for batteries, which is 50,000 to 95,000.
(9) The battery insulating member according to any one of (1) to (8), wherein the proportion of the (a) polyphenylene sulfide resin in the resin composition is 95% by weight or more. Element.
(10) The battery insulating member according to any one of (1) to (9), which has a weld line.
(11) The method for manufacturing a battery insulating member according to any one of (1) to (10), wherein the battery insulating member is injection-molded from the resin composition.

According to the present invention, it is possible to obtain an insulating member for a battery made of a polyphenylene sulfide resin composition having excellent hydrogen fluoride acidity, chemical resistance, caulking resistance, toughness of a welded portion, and heat resistance.

It is a schematic diagram of the molded product used for the evaluation of the caulking resistance.

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

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

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

Since the PPS copolymer having a part of such a structure has a melting point lower than the general melting point of 280 ° C. of PPS, such a resin composition is advantageous in terms of moldability.

The weight average molecular weight of the (a) PPS resin used in the present invention is not particularly limited, but the weight average molecular weight is preferably 30,000 to 150,000, more preferably 40,000 to 130,000, and further preferably 45,000 to 110,000 from the viewpoint of obtaining more excellent mechanical properties. Is more preferable, and 50,000 to 90000 is more preferable. When the weight average molecular weight is small, the mechanical properties of the PPS resin itself are deteriorated, so that it is preferably 30,000 or more. On the other hand, when the weight average molecular weight exceeds 150,000, the melt viscosity becomes remarkably large, which is not preferable in the molding process.

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

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

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

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

The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1. The range of 5 mol, more preferably 1.005 to 1.2 mol, can be exemplified.

[Sulfidating agent]
Sulfides include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Polymerization stabilizer]
Polymerization stabilizers can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesired side reactions. One guideline for side reactions is the production of thiophenols, and the addition of a polymerization stabilizer can suppress the production of thiophenols. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. The alkali metal carboxylate described above also acts as a polymerization stabilizer. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent is used. Oxides can also be polymerization stabilizers.

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

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

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

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

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

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

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

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

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

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

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

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

The conversion rate of the polyhalogenated aromatic compound (abbreviated as PHA here) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.

(A) When the polyhalogenated aromatic compound is excessively added to the alkali metal sulfide in terms of molar ratio, conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)) -PHA excess (mol)].

(B) In cases other than the above (A) Conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)].

[Recovery process]
(A) In the method for producing a PPS resin, a solid substance is recovered from a polymerization reaction product containing a polymer, a solvent and the like after the completion of polymerization. As for the recovery method, it is indispensable to adopt a method of recovering the particulate polymer by slowly cooling after the completion of the polymerization reaction. The slow cooling rate at this time is not particularly limited, but is usually about 0.1 ° C./min to 3 ° C./min. It is not necessary to slowly cool at the same rate in all the slow cooling steps, and a method of slowly cooling at a rate of 0.1 to 1 ° C / min until the polymer particles crystallize and precipitate, and then at a rate of 1 ° C / min or higher, etc. It may be adopted.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

From the viewpoint of improving the reactivity of the (a) PPS resin of the present invention with the (b) organic silane compound, it is also preferable that the PPS resin contains 25 to 400 μmol / g of a carboxyl group. The carboxyl group content is more preferably 25 to 250 μmol / g, further preferably 30 to 150 μmol / g, still more preferably 30 to 80 μmol / g. When the amount of the carboxyl group of the PPS resin is less than 25 μmol / g, (b) the reactivity with the organic silane compound tends to decrease, which is not preferable. On the other hand, when the carboxyl group content of the PPS resin exceeds 400 μmol / g, the amount of volatile components in the processing step increases, which is not preferable.

(A) As a method for introducing a carboxyl group into the PPS resin, a method for copolymerizing a polyhalogenated aromatic compound containing a carboxyl group or adding a compound containing a carboxyl group such as maleic anhydride or sorbic acid is added. Then, (a) a method of introducing by reacting with the PPS resin while melt-kneading can be exemplified.

(2) (b) Organic Silane Compound It is essential to add (b) an organic silane compound to the PPS resin composition constituting the insulating member for a battery of the present invention. Specific examples of the organic silane compound include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) Ureid group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanapropyltriethoxysilane, γ-isocyanapropyltrimethoxysilane, γ-isocyanapropylmethyldimethoxysilane, γ-isoxapropylmethyldiethoxysilane, γ-isocyanate. Isocyanate group-containing alkoxysilane compounds such as propylethyldimethoxysilane, γ-isocyanapropylethyldiethoxysilane, γ-isocyanapropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl). ) Organic silane compounds such as amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane can be mentioned. Among them, from the viewpoint of reactivity, epoxy group-containing alkoxysilane compounds and amino group-containing compounds can be mentioned. An alkoxysilane compound and an isocyanate-containing alkoxysilane compound are preferable, and an isocyanate group-containing alkoxysilane compound is particularly preferable. Excellent reactivity means that it leads to the development of excellent toughness after hydrofluoric acid treatment.

The amount of the organic silane compound added is preferably 0.2 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total PPS resin composition. Further, 0.2 to 2 parts by weight is preferable. When the amount of the organic silane compound added is 0.2 parts by weight or more, excellent toughness after hydrofluoric acid treatment can be sufficiently obtained, and burrs and mold stains during molding can be suppressed. .. By adding the amount of the organic silane compound to 5 parts by weight or less, the effect of improving toughness can be obtained, but the amount of gas generated can be suppressed, so that mold stains do not occur and the remarkable increase in melt viscosity can be suppressed, so that the thickness is thin. Even an insulating member for a battery having a shape can be easily injection-molded, which is preferable.

(3) (c) Polyolefin monomer or polyolefin copolymer containing 80 wt% or more of an olefin component The PPS resin composition constituting the insulating member for a battery of the present invention contains (c) a polyolefin containing 80 wt% or more of an olefin component. The content of the monomer or polyolefin copolymer is preferably less than 1 part by weight.

For example, by blending polyethylene as a polyolefin monomer and improving the mold releasability during injection molding, the molding cycle can be shortened, and the molding processability can be expected to be improved. On the other hand, when the blending amount is 1 part by weight or more, it is not preferable because it leads to the generation of gas during the molding process and the stain on the mold. Examples of the polyolefin monomer include, in addition to polyethylene, polymers of alkene such as polypropylene, polybutylene, polyisobutylene, polypentene, and polymethylpentene.

Further, in general, (a) a thermoplastic elastomer, which is a kind of polyolefin copolymer, is blended for the purpose of improving the toughness of the PPS resin. However, in the present invention, it is preferable to avoid blending the polyolefin copolymer as much as possible in order to obtain good caulking resistance, toughness at the weld portion, and molding processability. The polyolefin copolymer exists as an island component in the sea phase made of PPS resin, but the presence of a resin component other than the PPS resin, which is an island component, contributes to a decrease in adhesion at the weld portion and a decrease in toughness. It is preferable that the blending amount of the component (c) is in the above range because it is considered to be inviting.

Examples of such polyolefin copolymers include ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, and ethylene-methyl acrylate copolymers. Polymers, ethylene-ethyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-styrene copolymers, ethylene-methyl acrylate- Examples thereof include a glycidyl methacrylate copolymer, an ethylene-ethyl acrylate-glycidyl methacrylate copolymer, and an ethylene-vinyl acetate-glycidyl methacrylate copolymer.

It is also preferable that the polyolefin copolymer used in the present invention contains a reactive functional group from the viewpoint of (a) forming an intermolecular bond with the PPS resin.

The reactive functional group of the polyolefin copolymer is not particularly limited, and specifically, a vinyl group, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, an aldehyde group, a carbonyldioxy group and a haloformyl group. , Alkoxycarbonyl group, amino group, hydroxyl group, styryl group, methacrylic group, acrylic group, ureido group, mercapto group, sulfide group, isocyanate group, hydrolyzable silyl group and the like can be exemplified. Among them, hydroxyl group, epoxy group and carboxyl group. , Amino group, acid anhydride group and isocyanate group are preferable, and two or more of these reactive functional groups may be contained.

In the present invention, the content of (c) the polyolefin monomer or polyolefin copolymer containing 80 wt% or more of the olefin component is less than 1 part by weight with respect to 100 parts by weight of (a) the polyphenylene sulfide resin. Is more preferable, less than 0.8 parts by weight is more preferable, and less than 0.5 parts by weight is further preferable. Further, it is particularly preferable not to blend the polyolefin copolymer. When the content of the polyolefin copolymer exceeds 1 part by weight, the volatile components of the PPS resin composition at the time of heating and melting increase, which is not preferable from the viewpoint of electrolyte resistance and molding processability.

(4) (d) Other Additives Further, the PPS resin composition constituting the insulating member for a battery of the present invention contains (a) a PPS resin and (c) an olefin component as long as the effects of the present invention are not impaired. A resin other than the polyolefin monomer or the polyolefin copolymer containing 80 wt% or more may be added and blended.

Specific examples thereof include polyamide, polybutylene terephthalate, polyethylene terephthalate, polyketone, liquid crystal polymer, polyether ketone, polyether ether ketone, fluororesin (polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE). ), Tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride ( PVDF), polychlorotrifluoroethylene (PCTFE)) can be exemplified, but the present invention is not limited thereto. The amount of the resin added is preferably less than 15 parts by weight, more preferably less than 10 parts by weight, and particularly preferably less than 5 parts by weight, based on 100 parts by weight of the total PPS resin composition. Since it is considered that the presence of a resin component other than the PPS resin, which is an island component, contributes to a decrease in adhesion at the welded portion and causes a decrease in toughness, it is preferable that the blending amount of the other resin is within the above range.

In the PPS resin composition constituting the insulating member for a battery of the present invention, it is preferable that the amount of the oxoacid metal salt of phosphorus is less than 0.01 part by weight with respect to 100 parts by weight of (a) PPS resin. , More preferably less than 0.005 parts by weight. By blending the oxo acid metal salt of phosphorus, (c) the oxidative decomposition of the polyolefin monomer or polyolefin copolymer containing 80 wt% or more of the olefin component can be suppressed, and the mold stain during the molding process can be suppressed. This is because if the blending amount is 0.01 parts by weight or more, the melt viscosity of the PPS resin composition increases remarkably, which is not preferable in the molding process of the insulating member for a battery having a thin wall shape. Most preferably, it does not contain the oxoacid metal salt of phosphorus.

Examples of the oxo acid metal salt of phosphorus include hypophosphorous acid, phophosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, diphosphate and triphosphate. Specifically, potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, potassium phosphinate, sodium phosphinate, calcium phosphinate, aluminum phosphinate, aluminum diethylphosphinate, zinc phosphinate, magnesium phosphite, etc. Can be mentioned.

Further, the following compounds can be added for the purpose of modification. Polyalkylene oxide oligoma compounds, thioether compounds, ester compounds, organic phosphorus compounds and other plasticizers, organic phosphorus compounds, polyether ether ketones and other crystal nucleating agents, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, and other usual additives such as water, lubricants, UV inhibitors, anticolorants, colorants, foaming agents, etc. Can be compounded. If any of the above compounds exceeds 10 parts by weight of the entire composition, the original characteristics of the PPS resin composition of the present invention are impaired, so that it is not preferable, and it is preferable to add 5 parts by weight or less, more preferably 1 part by weight or less.

Further, in the present invention, a compatibilizer can be used in combination for the purpose of enhancing the compatibility between the resins. Specifically, an epoxy resin can be exemplified. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, special skeleton bifunctional epoxy resin having a biphenyl skeleton, naphthalene skeleton, etc., cresol novolak type, trisphenol methane type, and di. Glycidyl ether type epoxy resin typified by polyfunctional epoxy resin such as cyclopentadiene type, glycidylamine type epoxy resin typified by aromatic amine type and aminophenol type, and typified by hydrophthalic acid type and dimer acid type. A glycidyl ester type epoxy resin can be mentioned.

The amount of the epoxy resin added is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total PPS resin composition.

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

The blending amount of the inorganic filler is selected in the range of less than 30 parts by weight, preferably less than 10 parts by weight, more preferably less than 5 parts by weight, based on 100 parts by weight of the total PPS resin composition. A range of 1 part by weight or less is more preferable. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. The blending of the inorganic filler is effective for improving the strength of the material, but the blending of more than 30 parts by weight causes a decrease in toughness, which is not preferable.

(5) Method for Producing Resin Composition As a method for producing the PPS resin composition constituting the insulating member for a battery of the present invention, production in a molten state, production in a solution state, or the like can be used, but it is simple. From the viewpoint, production in a molten state is preferably used. For production in the molten state, melt-kneading by an extruder, melt-kneading by a kneader, or the like can be used, but from the viewpoint of productivity, melt-kneading by an extruder capable of continuously producing is preferably used. For melt kneading with an extruder, at least one extruder such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, or a twin-screw single-screw compound extruder can be used, but kneading property is possible. From the viewpoint of improving reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt-kneading by the twin-screw extruder is most preferable.

A more specific method for melt-kneading is not necessarily limited to this, but the L / D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more, and is kneading. It is preferable to use a twin-screw extruder having two or more parts, preferably three or more parts. The upper limit of L / D is not particularly limited, but 60 or less is preferable from the viewpoint of economy. Further, the upper limit of the number of kneading portions is not particularly limited, but it is preferably 10 or less from the viewpoint of productivity. The ratio of the kneading portion to the total length of the screw is preferably 15% or more, more preferably 20% or more, still more preferably 30% or more. When the ratio of the kneading portion to the total length of the screw is less than 15%, the kneading power is inferior, so that (c) the number average dispersion diameter of the polyolefin monomer or polyolefin copolymer containing 80 wt% or more of the olefin component becomes coarse. It is difficult to develop desired physical properties. On the other hand, the upper limit of the ratio of the kneading portion to the total length of the screw is preferably 70% or less from the viewpoint of preventing deterioration of the resin due to the generation of excessive shearing heat generation during kneading.

As for the screw rotation speed, a method of kneading under the conditions of 150 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute, and more preferably 350 to 800 rotations / minute is preferable. When the screw rotation speed exceeds 150 rotations / minute, the kneading force is sufficient, so that (c) the number average dispersion diameter of the polyolefin monomer or polyolefin copolymer containing 80 wt% or more of the olefin component becomes finer, which is desired. It leads to the development of toughness. (B) Since the reaction occurs sufficiently even when the organic silane compound is added, it leads to the development of desired toughness and mold stainability. When the screw rotation speed exceeds 1000 rpm, deterioration of the resin and additives occurs due to excessive shear heat generation during kneading, resulting in deterioration of toughness, mold stainability, and burrs due to a decrease in melt viscosity. It is not preferable because it leads to deterioration of molding processability. Further, by setting a large screw rotation speed within this range, the melt viscosity can be reduced while maintaining the toughness, so that the fluidity of the thin-walled insulating member for a battery during injection molding is improved. This is a preferable tendency from the viewpoint of moldability.

The preferred cylinder temperature (° C.) range is (a) a temperature range of + 5 to 100 ° C., more preferably a range of 280 to 400 ° C., relative to the melting point of 250 to 280 ° C. of the PPS resin. The range of 280 to 360 ° C. is more preferable, and the range of 280 to 330 ° C. is even more preferable.

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

(6) PPS Resin Composition In the PPS resin composition constituting the insulating member for a battery of the present invention, a test piece (ISO527-2-1A) obtained by injection molding is converted into hydrofluoric acid (50% aqueous solution). In a tensile test (ISO527-1, 2) after immersion under 60 ° C. conditions for 500 hours, the tensile elongation at break is 5% or more (experimental conditions are 23 ° C., tensile speed 50 mm / min, The distance between chucks is 114 mm). 6% or more is more preferable, and 7% or more is more preferable. The tensile elongation at break of the test piece after immersion in hydrofluoric acid in the tensile test is 5% or more, which means that the insulating member for a battery made of the PPS resin composition has excellent resistance to hydrofluoric acid. It is indispensable from the viewpoint of ensuring safety because the deterioration of the material can be suppressed and the insulating property can be maintained even if the insulating member for a battery is exposed to hydrofluoric acid generated in practical use. The upper limit of the tensile elongation at break in the tensile test after immersion in hydrofluoric acid is preferably as high as possible, and there is no particular limitation, but the upper limit is substantially about 200%. In order to obtain a PPS resin composition having such tensile elongation at break after immersion in hydrofluoric acid, a method of adding an organic silane compound to the PPS resin or adding other components other than the organic silane compound as much as possible. The method of not using can be exemplified as a preferable method.

The PPS resin composition constituting the insulating member for a battery of the present invention is a test piece having a thickness of 1.6 mm, a width of 6 mm, and a distance between marked lines of 50 mm in which a weld portion is formed in the central portion between marked lines obtained by injection molding. In a tensile test measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min (hereinafter, a tensile test using a test piece having such a welded portion may be referred to as a weld tensile test). The tensile strength represented by the area under the curve is preferably 100 MPa ·% or more. 150 MPa ·% or more is more preferable, and 200 MPa ·% or more is more preferable. The tensile volume is represented by the area under the stress-strain curve in the tensile test, can be used as strain fracture energy up to the breaking point in the tensile test, and is an index of so-called toughness. Specifically, for example, the tensile product can be calculated by integrating the area under the stress-strain curve with the stress value in the stretched state every 0.04% of the elongation rate. The tensile strength of the weld tensile test is 100 MPa ·% or more, which means that the toughness of the weld portion is excellent. It is preferable from the viewpoint of ensuring safety because it can suppress damage during actual use and maintain insulation. The upper limit of the tensile strength of the weld tensile test is preferably as high as possible, but there is no particular limitation, but the upper limit is substantially 1000 MPa ·%. In order to obtain a PPS resin composition having such a tensile strength, a method of adding an organic silane compound to the PPS resin and a method of adding as little other components as possible other than the organic silane compound are exemplified as preferable methods. can.

The PPS resin composition constituting the insulating member for a battery of the present invention is a test piece having a thickness of 1.6 mm, a width of 6 mm, and a distance between marked lines of 50 mm in which a weld portion is formed in the central portion between marked lines obtained by injection molding. In a tensile test measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min, the tensile elongation at break (%) is 3.0% or more, preferably 4.0% or more, and more preferably 5.0% or more. .. A tensile breaking elongation of 3.0% or more in the weld tensile test means that the toughness of the weld portion is excellent, and when the shape of the insulating member for a battery is used, a load is applied in the caulking process during battery manufacturing. Since damage is suppressed when the battery is stretched, it is preferable from the viewpoint of improving the yield in the production process and ensuring the safety in the actual use environment. The upper limit of the tensile elongation at break in the weld tensile test is preferably as high as the elongation, and there is no particular limitation, but the upper limit is substantially 100%. The tensile strength in the test is preferably 60 MPa or more, more preferably 65 MPa or more, and even more preferably 70 MPa or more. A tensile strength of 60 MPa or more in the weld tensile test means that damage to the weld, which is the most fragile part of the molded product, can be suppressed, and it is possible to deal with thinning and complication of the molded product in the design of the member. It is preferable because it can be done. The upper limit of the tensile strength of the weld tensile test is preferably as high as possible, and there is no particular limitation, but the upper limit is substantially about 300 MPa.

The PPS resin composition constituting the insulating member for a battery of the present invention is a test piece having a thickness of 1.6 mm, a width of 6 mm, and a distance between marked lines of 50 mm in which a weld portion is formed in the central portion between marked lines obtained by injection molding. In the tensile test measured under the condition of a tensile speed of 10 mm / min in an atmosphere of 80 ° C., the tensile strength is preferably 45 MPa or more, more preferably 50 MPa or more. It is preferable that the tensile strength in the weld tensile test in an atmosphere of 80 ° C. is 45 MPa or more because the strength as an insulating member for a battery can be maintained even in a high temperature environment during actual use of the battery, and deformation and breakage can be suppressed. .. The upper limit of the tensile strength in the weld tensile test in an atmosphere of 80 ° C. is preferably as high as possible, and there is no particular limitation, but the upper limit is substantially about 200 MPa.

The melt viscosity (temperature 320 ° C., shear rate 2432 / s) of the PPS resin composition constituting the insulating member for a battery of the present invention is preferably 250 Pa · s or less, more preferably 200 Pa · s or less, still more preferably 180 MPa. It is preferable that the melt viscosity is 250 Pa · s or less from the viewpoint of molding processability of the thin-walled insulating member for a battery. If the melt viscosity exceeds 250 Pa · s, the moldability is deteriorated. The lower limit of the melt viscosity is preferably 10 Pa · s or more because it leads to the generation of burrs during the molding process. In order to obtain a PPS resin composition having such a melt viscosity, a method of using a PPS resin having a molecular weight in a specific range as a raw material or a method of kneading a PPS resin and an organic silane compound at a high rotation speed during melt kneading. Can be exemplified.

Further, the fluidity of the PPS resin composition constituting the insulating member for a battery of the present invention is the flow length (1 mm thickness, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection) in the spiral flow mold. The pressure (pressure 98 MPa, injection time 5 sec, cooling time 15 sec) is preferably 100 mm or more, more preferably 115 mm or more, still more preferably 130 mm or more. The larger this value is, the better the liquidity is. A flow length of 100 mm or more is preferable from the viewpoint of moldability of the thin-walled insulating member for a battery. If the flow length is less than 100 mm, the molding processability is deteriorated. As for the upper limit of the flow length, a higher value is preferable, and there is no particular limitation, but the upper limit is substantially about 300 mm.

The PPS resin composition constituting the insulating member for a battery of the present invention has a molecular weight distribution obtained from the measurement of gel permeation chromatography (GPC) of the resin composition, which is faster than the elution time corresponding to the polystyrene-equivalent molecular weight of 750000. The ratio of the detected component (hereinafter, may be referred to as component (X)) is 0.4 to 8.5%, and the component detected later than the elution time corresponding to the polystyrene-equivalent molecular weight of 750000 (hereinafter, may be referred to as component (X)). It is preferable that the weight average molecular weight of (may be referred to as “component (Y)”) is 50,000 to 95,000. By setting the ratio of the component (X) and the weight average molecular weight of the component (Y) in the above range, both the excellent toughness of the insulating member for a battery and the melt viscosity suitable for the thin-walled molding process are exhibited. It is preferable because it leads to. The ratio of the component (X) is preferably 0.5 to 8.0%, more preferably 0.5 to 7.5%. The weight average molecular weight of the component (Y) is preferably 60000 to 90000, more preferably 65000 to 85000. The ratio of the component (X) and the weight average molecular weight of the component (Y) are both indicators of the amount of high molecular weight compound produced by the reaction in the extruder, and when the ratio of the component (X) exceeds 8.5%. Since the reaction between the PPS resin and the components other than the PPS resin contained therein is excessive, the melt viscosity becomes remarkably high, which leads to a decrease in molding processability. If it is less than 0.4%, it may be difficult to develop the desired toughness, or it may lead to the generation of burrs during molding and the generation of mold stains due to low molecular weight components. If the weight average molecular weight of the component (Y) is less than 50,000, it means that the molecular weight of the PPS resin in the PPS resin composition is too small, and it is difficult to develop the desired toughness. If it exceeds 95,000, the PPS resin composition Since the molecular weight of the PPS resin in the resin is too large, it means that the melt viscosity is high, which leads to a decrease in molding processability. In order to keep the ratio of the component (X) and the weight average molecular weight of the component (Y) in the above range, the weight average molecular weight is 50,000 to 90000 in the melt kneading of the PPS resin and the organic silane compound using a twin-screw extruder. A method of kneading at a high rotation speed using the PPS resin of No. 1 can be exemplified.

Here, "the ratio of the component detected earlier than the elution time corresponding to the molecular weight 750000" means the component having a molecular weight of 7.50000 or more in terms of polystyrene when the total area area of the GPC elution curve is 100%. It is the ratio of the corresponding area area.

In the PPS resin composition constituting the insulating member for a battery of the present invention, the proportion of (a) PPS resin in the PPS resin composition is 95% by weight or more from the viewpoint of toughness of the weld portion and moldability. It is more preferably 97% by weight or more, and even more preferably 98% by weight or more.

(7) Insulating member for battery The insulating member for a battery made of the PPS resin composition of the present invention refers to an insulating member for a primary or secondary battery, and is between a pair of terminals in the primary or secondary battery. It is used to prevent an internal short circuit in the battery. Primary or secondary batteries include alkaline manganese dry batteries, galvanic batteries, nickel-based primary batteries, lithium batteries, manganese dry batteries, mercury batteries, all-solid-state batteries and other primary batteries, lead storage batteries, lithium / air batteries, and lithium ions. 2 such as secondary battery, lithium ion polymer secondary battery, iron phosphate lithium ion battery, lithium / sulfur battery, nickel / cadmium storage battery, nickel / hydrogen rechargeable battery, nickel / lithium battery, nickel / zinc battery, all-solid-state battery, etc. The next battery is mentioned.

Examples of the insulating member for a battery include an insulating plate, a gasket, a terminal holder, a case, an insulating ring, an insulating tube and the like. Since the insulating member for a battery made of the PPS resin composition of the present invention has excellent toughness even in the weld portion generated by injection molding or the like, the risk of damage in the weld portion can be greatly reduced. Application to gaskets, terminal holders, and cases is preferable, and application to insulating plates is particularly preferable from the viewpoint of the risk of direct connection to an internal short circuit.

The insulating member for a battery of the present invention can be molded by various molding methods such as injection molding, extrusion molding, compression molding, injection molding, injection compression molding, and injection molding is particularly preferable from the viewpoint of productivity. However, when the insulating member for a battery is molded by injection molding, an annular molten resin flow occurs in an opening or the like into which a terminal or a lid is fitted, and a weld is formed in a portion where two or more resin flows meet. A vulnerable part called is formed. At the time of battery manufacturing, a fitting process of assembling the terminals of the positive and negative of the battery with the lid, gasket and insulating plate is provided, and the so-called "caulking process" of striking or tightening the joint is used for fitting. When an insulating plate or gasket having a welded portion obtained is used, the welded portion may be cracked due to the load on the molded product in the caulking process at the time of fitting, and the welded portion may not play the role of the insulating plate or gasket. .. For such a manufacturing process, in the present invention, when the insulating member for a battery has a welded portion, the welded portion does not cause damage even if it follows the deformation such as stretching (strain). It was found that the property of (destructive energy) is important.

It is preferable that the insulating member such as the insulating plate made of the PPS resin composition of the present invention has excellent caulking resistance. The caulking resistance can be evaluated by the following method. The battery insulating member having the opening shown in FIG. 1 is injection molded by injection molding, and the damage state when the battery insulating member is bent 90 degrees with the weld line as the center line is evaluated according to the following criteria. It is used as an index of caulking resistance. When 10 samples were evaluated, the level of zero breaks and cracks was ◎, the level of zero breaks and cracks was 1 or more, and the level of 3 or less was ○, the level of zero breaks and cracks was 4 or more, and 10 samples. The following levels are Δ, and the sample in which even one sample is broken is judged to be ×.

The battery insulating member made of the PPS resin composition of the present invention has excellent resistance to hydrofluoric acid. The evaluation of resistance to hydrofluoric acid can be carried out as follows. A test piece (ISO527-2-1A) was molded by injection molding, and the weight change rate before and after immersion when immersed in hydrofluoric acid (50% aqueous solution) under 60 ° C. conditions for 500 hours was calculated by the following formula. evaluate. The weight change rate is calculated and evaluated as an absolute value.
Weight change rate (%) = | (Molded product weight after treatment-Molded product weight before treatment) / Weight before treatment | × 100 (%)
The rate of change in weight before and after immersion in hydrofluoric acid is preferably 2% or less, more preferably 1.5% or less, and even more preferably 1.2% or less. It is preferable that the weight change rate before and after immersion in hydrofluoric acid is 2% or less from the viewpoint of suppressing deterioration of the battery insulating member. If the rate of change in weight before and after immersion in hydrofluoric acid exceeds 2%, it means that the resin material deteriorates, decomposes or swells, and the mechanical properties as a structural member for a battery deteriorate, which is not preferable. .. The lower limit of the rate of change in weight before and after immersion in hydrofluoric acid is preferably as small as the amount of change, and there is no particular limitation, but the lower limit is substantially 0.001%.

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

In Examples and Comparative Examples, (a) a PPS resin, (b) an organic silane compound, (c) a polyolefin monomer or a polyolefin copolymer containing 80 wt% or more of an olefin component, and (d) other additives as described below. I used the one.

[(A) PPS resin (a-1, a-2)]
a-1: Linear PPS resin Weight average molecular weight: 70000, number average molecular weight: 23000, carboxyl group amount: 33 μmol / g, melting point: 280 ° C.
a-2: Linear PPS resin Weight average molecular weight: 42000, number average molecular weight: 16000, carboxyl group amount: 42 μmol / g, melting point: 280 ° C.

[(B) Organic silane compound (b-1, b-2, b-3)]
b-1: γ-Isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007N).
b-2: γ-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903)
b-3: 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303)

[(C) Polyolefin monomer or polyolefin copolymer containing 80 wt% or more of olefin component (c-1, c-2)]
c-1: Polyethylene (manufactured by Prime Polymer Co., Ltd., PE7000FP), melting point 130 ° C.
c-2: Ethylene-glycidyl methacrylate copolymer (olefin resin manufactured by Sumitomo Chemical Co., Ltd., Bond First E, melting point 103 ° C., MFR: 3 g / 10 minutes (190 ° C., 21.2 N load)), reactive functional group amount: 12% by weight

[(D) Other additives (d-1, d-2, d-3)]
d-1: Polyester sulfone resin (manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel SE4800G), glass transition temperature: 225 ° C.
d-2: Glass fiber (T-747 manufactured by Nippon Electric Glass Co., Ltd.), average fiber diameter 13 μm
d-3: Sodium phosphinate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
In the following examples, the material properties were evaluated by the following method.

[Tensile test after immersion in hydrofluoric acid]
An injection molding machine (manufactured by Sumitomo Heavy Industries: SE75DUZ) was used to mold a test piece conforming to ISO527-2-1A under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. The obtained test piece was immersed in hydrofluoric acid (50% aqueous solution) in a PFA container and treated under 60 ° C. conditions for 500 hours. A tensile test (ISO527-1, 2) was performed on the immersed test piece under the conditions of atmosphere: 23 ° C., tensile speed: 50 mm / min, and chuck distance of 114 mm, and tensile elongation at break (nominal strain) was evaluated. ..

[Weld tensile test]
Using an injection molding machine (manufactured by Sumitomo Heavy Industries: SE75DUZ), injection molding was performed under the conditions of a cylinder temperature of 300 ° C and a mold temperature of 150 ° C. Part shape: thickness 1.6 mm, width 6 mm, distance between marked lines 50 mm) was obtained. Using the obtained test piece, a tensile test was performed under the conditions of a temperature of 23 ° C. and a tensile speed of 10 mm / min, and tensile elongation at break, tensile strength, and tensile strength were evaluated. The tensile product was calculated by integrating the stress value in the area under the stress-strain curve at every 0.04% elongation.

[Weld tensile test at 80 ° C]
Tensile dumbbell pieces prepared by the same method as those used in the weld tensile test were subjected to a tensile test under the conditions of a temperature of 80 ° C. and a tensile speed of 10 mm / min, and the tensile strength was evaluated.

[Melting viscosity]
The melt viscosity of the PPS resin composition is a value measured using a capillograph manufactured by Toyo Seiki under the conditions of 320 ° C. and a shear rate of 2432 / s. A capillary having a length of 10 mm and a diameter of 1 mm was used for the measurement.

[GPC measurement]
From the weight average molecular weight and number average molecular weight of the PPS resin composition and PPS resin calculated in terms of polystyrene using gel permeation chromatography (GPC), and the elution time corresponding to the molecular weight of the PPS resin composition in terms of polystyrene of 750000. The proportion of the component (X) detected earlier and the weight average molecular weight of the component (Y) detected later than the elution time corresponding to the molecular weight 750000 were determined. , The measurement conditions of GPC are shown below.
Equipment: SSC-7110 (Senshu Science)
Column name: Shodex UT806M x 2
Eluent: 1-Chloronaphthalene detector: Differential refractive index detector Column temperature: 210 ° C
Pre-constant temperature bath temperature: 250 ° C
Pump constant temperature bath temperature: 50 ° C
Detector temperature: 210 ° C
Flow rate: 1.0 mL / min
Sample injection amount: 300 μL (slurry: about 0.2% by weight).

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

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

[Liquidity (spiral flow)]
Using a 1 mm thick spiral flow mold, molding was performed under the conditions of cylinder temperature 320 ° C, mold temperature 140 ° C, injection speed 230 mm / sec, injection pressure 98 MPa, injection time 5 sec, and cooling time 15 sec, and the flow length was measured. (Injection molding machine used: "SE-30D" manufactured by Sumitomo Heavy Industries).

[Crimping resistance]
Cylinder temperature: 320 ° C, mold temperature: 130 ° C, injection speed: 100 mm / s, injection pressure is set within 50-80 MPa so that the filling time is 0.4 seconds, and injection molding is performed (molding used). Machine: "SE75DUZ-C250" manufactured by Sumitomo Heavy Industries, Ltd.), Insulation member for battery having an opening shown in FIG. 1 (size; length: 55 mm, width: 20 mm, thickness: 2 mm, opening size: 6 mmφ, weld line : 2 mm) was obtained.

With the weld line of the obtained battery insulating member as the center line, the damage state when the battery insulating member was bent 90 degrees was evaluated according to the following criteria. When 10 samples were evaluated, the level of zero breaks and cracks was ◎, the level of zero breaks and cracks was 1 or more, and the level of 3 or less was ○, the level of zero breaks and cracks was 4 or more, and 10 samples. The following levels were determined to be Δ, and samples in which even one sample was broken were judged to be ×.

[Hydrogen fluoride acid resistance (weight change rate before and after immersion in hydrofluoric acid)]
An injection molding machine (manufactured by Sumitomo Heavy Industries: SE75DUZ) was used to mold a molded product conforming to ISO527-2-1A under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. The weight of the obtained molded product was measured and used as the weight before processing. Then, the molded product was immersed in hydrofluoric acid (50% aqueous solution) in a PFA container and treated under 60 ° C. conditions for 500 hours. After the treatment, the aqueous solution on the surface was removed, and then the weight of the molded product was measured and used as the weight after the treatment. The weight change rate was calculated as an absolute value of (weight of molded product after treatment-weight of molded product before treatment) / weight before treatment × 100 (%).

[Examples 1 to 4, 6 to 8, Comparative Examples 1, 3 to 7]
(A) PPS resin, (b) organic silane compound, (c) polyolefin monomer or polyolefin copolymer containing 80 wt% or more of olefin component, (d) other additives were dry-blended at the ratio shown in Table 1. After that, using a TEX30α twin-screw extruder (30 mmφ, L / D = 45) manufactured by Japan Steel Works equipped with a vacuum vent, the screw arrangement was made at 3 kneading parts, and the ratio of the kneading part to the total length of the screw was 30%. The cylinder temperature was set to 320 ° C. and the screw rotation speed was set to 300 rpm for melt-kneading. Let A be the melt-kneading method under this condition. Then, it was pelletized by a strand cutter. The obtained pellets were dried at 130 ° C. overnight and then used for measuring the melt viscosity and GPC. The obtained pellets were subjected to injection molding, and hydrofluoric acid immersion test, weld characteristics, moldability, and caulking resistance were evaluated. The results are as shown in Tables 1 and 2.

[Example 5]
The resin composition pellets were obtained by melt-kneading under the same conditions as in Example 1 except that the screw rotation speed was set to 500 rpm and melt-kneaded, and various characteristics were evaluated. Let B be the melt-kneading method under this condition. The results are as shown in Table 1.

[Comparative Example 2]
A side feeder was installed at a position 45% of the total length of the screw, and glass fibers were charged using the side feeder. The characteristics were evaluated. Let C be a melt-kneading method under this condition. The results are as shown in Table 2.

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

In Examples 1 to 8, the PPS resin composition containing (a) a PPS resin and (b) an organic silane compound has excellent tensile elongation at break and practical characteristics after the hydrofluoric acid immersion treatment. The small change in weight before and after the hydrofluoric acid immersion treatment was exhibited. In addition, excellent tensile strength was also exhibited in the weld tensile test, and there was a tendency for the tensile elongation at break of the weld portion to be improved as compared with the comparative example. In the examples, since the characteristics of the weld portion are excellent, the caulking resistance as an insulating member is good.

(C) In Examples 3 and 4 to which the olefin copolymer and other additives were added, the weight change before and after the hydrofluoric acid treatment tended to be larger than in Examples 1 and 2. .. In addition, the tensile strength and the weld tensile elongation at break in the weld tensile test tended to decrease, and the caulking resistance tended to decrease.

On the other hand, in Comparative Examples 1 to 6, the tensile elongation at break after the hydrofluoric acid immersion treatment was small, and the results were inferior to the acid resistance to hydrogen fluoride. Comparative Example 2 could not be measured because the shape of the test piece was not retained after the immersion treatment.

Further, in Comparative Examples 1 to 6, the tensile strength in the weld tensile test was as small as 100 MPa ·% or less, the toughness was low, and the molded product was broken in the caulking resistance test. It is presumed that the reason for such a result is that the organic silane compound was not used in Comparative Example 1. Since glass fiber was used in Comparative Example 2, the toughness was extremely lowered. In Comparative Examples 3 to 5 using the PPS resin having a low molecular weight, the ratio of the component (X) in the GPC measurement was low, and the weight average molecular weight of the component (Y) was also small. In Comparative Example 5 in which 0.1 part by weight of the organic silane compound was blended, almost no effect of adding the organic silane compound was observed. On the other hand, in Comparative Example 7 in which 10 parts by weight of the organic silane compound was blended, the resin composition was remarkably thickened, and the molded product could not be molded by injection molding.

1. 1. Molded product for evaluation of caulking resistance 2. Gate 3. Opening 4. Weld line

Claims (11)

A test piece obtained by injection molding the insulating member for a battery, wherein the insulating member comprises (a) a polyphenylene sulfide resin and (b) a polyphenylene sulfide resin composition containing an organic silane compound. (ISO527-2-1A) has a tensile elongation at break of 5% or more in a tensile test (ISO527-1 and 2) after being immersed in hydrofluoric acid (50% aqueous solution) under 60 ° C. conditions for 500 hours. Insulation member for batteries. The battery insulating member according to claim 1, wherein a test piece (ISO527-2-1A) obtained by injection molding the resin composition is added to hydrofluoric acid (50% aqueous solution) under 60 ° C. conditions. A battery insulating member having a weight change rate of 2% or less before and after immersion after immersion for 500 hours. The battery insulating member according to claim 1 or 2, which is obtained by injection molding the resin composition and has a weld portion formed in a central portion between marked lines, having a thickness of 1.6 mm, a width of 6 mm, and a marked line. In a tensile test of a test piece with a distance of 50 mm measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min, the tensile strength expressed by the area under the curve of the stress-strain curve is 100 MPa ·% or more for battery insulation. Element. The insulating member for a battery according to any one of claims 1 to 3, wherein a weld portion is formed in a central portion between marked lines, which is obtained by injection molding the resin composition, and has a thickness of 1.6 mm and a width of 6 mm. , A battery insulating member having a tensile elongation at break of 3.0% or more in a tensile test measured under the conditions of 23 ° C. and a tensile speed of 10 mm / min for a test piece having a distance between marked lines of 50 mm. The battery insulating member according to any one of claims 1 to 4, wherein a test piece having a weld portion formed in a central portion between marked lines obtained by injection molding the resin composition under an atmosphere of 80 ° C. Insulation member for a battery having a tensile strength of 45 MPa or more at the time of a tensile test in. The insulating member for a battery according to any one of claims 1 to 5, wherein the resin composition contains (a) 80 wt% or more of an olefin component with respect to 100 parts by weight of (a) PPS resin. An insulating member for a battery having a content of a weight or a polyolefin copolymer of less than 1 part by weight. The battery insulating member according to any one of claims 1 to 6, wherein the melt viscosity (measurement conditions are temperature 320 ° C., shear rate 2432 / s) of the resin composition is 250 Pa · s or less. Insulation member for. The insulating member for a battery according to any one of claims 1 to 7, which corresponds to a polystyrene-equivalent molecular weight of 750000 in the molecular weight distribution obtained from the measurement of gel permeation chromatography (GPC) of the resin composition. The proportion of the component detected earlier than the elution time is 0.4 to 8.5%, and the weight average molecular weight of the component detected later than the elution time corresponding to the polystyrene-equivalent molecular weight of 750000 is 50,000 to 95,000. Insulation member for batteries. The battery insulating member according to any one of claims 1 to 8, wherein the proportion of the (a) polyphenylene sulfide resin in the resin composition is 95% by weight or more. The battery insulating member according to any one of claims 1 to 9, wherein the battery insulating member has a weld line. The method for manufacturing an insulating member for a battery according to any one of claims 1 to 10, wherein the insulating member for a battery is injection-molded from the resin composition.

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