TW201602217A - Battery case for lead-acid battery, lead-acid battery using the battery case, and resin composition for the battery case - Google Patents

Abstract

Provided herein are a battery case for a lead-acid battery, which is made of an ABS resin and provides a high impact resistance even if the processability and the flame retardance are sufficiently enhanced, a lead-acid battery using the battery case, and a resin composition for the battery case. A battery case for a lead-acid battery is formed from a resin material containing an ABS resin having a Charpy impact value of 20 kJ/m2 or more as a main component and an additive added in an adjusted amount and selected such that the battery case meets a flammability class of UL94V-0 and has a Charpy impact value of 10 kJ/m2 or more.

Description

Battery case for lead-acid battery, lead-acid battery using the same, and resin composition for the battery case

The present invention relates to a battery case for a lead-acid battery, a lead-acid battery using the battery case, and a resin composition for the battery case, and more particularly to a battery for a valve-regulated lead-acid battery A shell, a lead-acid battery using the battery case, and a resin composition for the battery case.

A valve-regulated lead-acid battery is used as an uninterruptible power supply, such as a backup power supply for portable devices, wireless devices, and computers; Fixed battery; the main power supply for electric vehicles; and the power supply for starting the engine of the car, which has the advantage of no maintenance and discharge of a little acid mist or gas. Valve-regulated lead-acid batteries are also used as industrial batteries, such as emergency power supplies for office buildings, hospitals, etc., for energy storage systems that balance electrical loads (reduce peak power, peak shifting) And the output for natural energy generators Settling device.

Lead-acid batteries are economical and have stable performance compared to other secondary batteries. Therefore, the demand for lead-acid batteries is increasing year by year. The properties required for lead-acid batteries, such as higher capacity, longer life, wider available temperature range, and lighter weight, have diversified depending on the application, and the required quality level has increased year by year.

A lead-acid battery is charged and discharged via a chemical reaction between a group of electrodes disposed in a battery can and dilute sulfuric acid used as an electrolyte. The dilute sulfuric acid exhibits strong acidity and electrolyte leakage is at risk. Therefore, it is necessary to pay sufficient attention to cracking, cracking, and deterioration of the battery can. Therefore, the battery case of a lead-acid battery requires high acid resistance and sulfate resistance.

If the battery case is cracked or cracked, the electrolyte may leak and endanger the surrounding equipment.

From the viewpoint of disaster prevention (fire prevention), a battery case for a lead-acid battery requires impact resistance, mechanical strength, flame retardancy, and high formability.

JP 2002-42748 A discloses a battery can made of flame-retardant polypropylene. JP2006-348098A discloses a lead-acid battery battery case made of a polycarbonate resin having mechanical strength, formability, and flame retardancy. JP 2008-519153 A discloses an acrylonitrile-butadiene-styrene copolymer resin composition (ABS resin composition) containing a bromine organic compound flame retardant, a lanthanum flame retardant auxiliary, and a stearylamine compound, Providing high flame retardancy also provides significantly improved weather resistance and thermal stability as well as improved impact strength and flow to improve processability.

A lead-acid battery installed in a base station such as a mobile phone is used as an emergency power supply when a commercial power supply is lost due to a disaster or the like. Therefore, such lead-acid batteries are required to allow continuous power supply without problems until the power supply is restored and the battery capacity to operate reliably. Especially in inconvenient areas, it is difficult to maintain lead-acid batteries frequently. Therefore, long-term safety and reliability are required. It is important that the fire should not spread to surrounding equipment even if it is caught by an abnormality in the power supply system or the lead-acid battery. Therefore, a battery case for a lead-acid battery requires the use of a resin material that conforms to the UL94V-0 flammability class and has self-extinguishing properties.

The battery case for a lead-acid battery may be damaged or recessed in some states when the lead-acid battery is transported to be installed at a predetermined position or to maintain a lead-acid battery. A battery case for a lead-acid battery may be cracked or cracked due to stress concentration in a damaged or recessed portion as the battery case expands and contracts as the day and night (time of day) or the ambient temperature fluctuates. Lead-acid batteries used as emergency power supplies are typically used in a fully charged state in an emergency. However, in order to check the capacitance of the lead-acid battery and check whether there is a problem in the lead-acid battery, the lead-acid batteries are discharged at intervals of a specific period for inspection. After the test, the lead-acid batteries are fully charged to restore the capacity to return to the standby state. When the lead-acid battery is charged and discharged for inspection, the lead-acid battery generates heat, so the battery case expands and contracts. Cracked or cracked.

It is conceivable that the lead-acid battery and surrounding devices are damaged by leakage current or spark generated by the electrolyte leaking from the broken portion of the battery can. If a lead-acid battery and a member accommodating the lead-acid battery are short-circuited through a broken portion of the battery case, the lead-acid battery may become hot, and a fire may occur in the battery case and surrounding devices. Surrounding area. Therefore, there is a need for a battery case having high impact resistance so that the battery case is not damaged or recessed even when the lead-acid battery is not carefully watched during the lead-acid battery delivery and maintenance.

Some ABS resins have high impact resistance. However, ABS resins having high impact resistance have low fluidity, thus reducing processability. Therefore, when a battery case for a lead-acid battery is formed from an ABS resin, an ABS resin having low impact resistance is inevitably used to maintain workability. When a flame retardant or the like is added to impart flame retardancy to the ABS resin, the impact resistance of the ABS resin is further lowered. Therefore, when a conventional ABS resin composition is used, the flame retardancy and impact resistance of the battery case for a lead-acid battery cannot be sufficiently enhanced.

An object of the present invention is to provide a battery case for a lead-acid battery made of an ABS resin which can provide high impact resistance even if the workability and flame retardancy are sufficiently enhanced, and a lead-acid battery using the battery case And a resin composition for the battery can.

In order to solve the aforementioned problems, the inventors of the present invention conducted a serious study and found that a battery case for a lead-acid battery having a Charpy impact value of 10 kJ/m ² or higher can be contained even if a flame retardant is added. It is obtained by using a resin material having a sand blast impact value of 20 kJ/m ² or more as a main component in accordance with the flammability rating of UL94V-0. Based on these findings, the inventors of the present invention conducted research on the use of fatty guanamine to enhance the processability of the resin material in combination with the use of brominated bisphenol A as a flame retardant and antimony trioxide as a flame retardant. As a result, it was found that the obtained battery can for a lead-acid battery provides good processability during formation, meets the flammability rating of UL94V-0, has a sand blast impact value of 10 kJ/m ² or higher, and is highly resistant to sulfate and Acid resistant. Thus, the present invention has been completed based on the above findings.

An object of the present invention is to improve a battery can for a lead-acid battery formed of a resin material containing an ABS resin as a main component and an additive containing a flame retardant. According to the present invention, a battery case for a lead-acid battery having a haw impact value of 10 kJ/m ² or more and having high processability can be obtained by including an additive containing a flame retardant so that UL94V-0 can be obtained. The high flammability rating is obtained by a resin material having a sand impact value of 20 kJ/m ² or more as the main component of the ABS resin.

The UL94 standard is a standard value for testing the flammability of plastic materials used in components of the device established by Underwriters Laboratories Inc. in the United States and is an internationally applicable safety standard.

The term "sand impact value" means a value measured at 25 ° C in the atmosphere according to JIS K 7111-1, specifically, the energy required to break the sample divided by the cross section before the sample is broken. The value obtained. With Shaying The larger the hit, the higher the tenacity or toughness of the sample and the more difficult it is to break.

One specific example of the resin material may contain brominated bisphenol A, antimony trioxide, and fatty acid amide added thereto as an additive. The combination of brominated bisphenol A, antimony trioxide, and fatty decylamine is a combination of additives which can sufficiently enhance the impact resistance, workability, and flame retardancy.

As used herein, "fat amide" includes stearic acid amide, bis-stearic acid amide, bis-hydroxystearic acid amide, and inter-extension M-xylylene-bis-stearic acid amide, N,N'-distearyl isophthalic acid amide, N,N' N,N'-distearyl sebacic acid amide, N,N'-distearyl adipic acid amide, butyl- Butyl-bis-hydroxystearic acid amide, hexamethylene-bis-hydroxystearic acid amide, hexamethylene-bis-alcodamine Hexamethylene-bis-behenic acid amide, hexamethylene-bis-stearic acid amide, ethylene-bis-behenic acid amide, Ethylene-bis-hydroxystearic acid amide, ethylene-bis-stearic acid amide, ethyl-bis-lauric acid Ethylene-bis-lauric acid amide ), Ethylene-bis-capric acid amide, ethylene-bis-caprylic acid amide, methylene-bis-hydroxystearic acid amide Methylene-bis-hydroxystearic acid amide), methylene-bis-lauric acid amide, and methylene-bis-stearic acid amide.

In one specific composition of the resin material, the additive may contain 15 to 25 parts by mass of brominated bisphenol A, 5 mass per 100 parts by mass of the ABS resin having a haw impact value of 20 kJ/m ² or more. Parts or more of antimony trioxide, and 0.1 part by mass or more of fatty amidoxime.

The fatty guanamine can be, for example, bis-stearylamine.

The ABS resin as a main component of the resin material preferably has a haw impact value of 25 kJ/m ² or more. This ensures that the cell impact value for the battery case of the lead-acid battery is 10 kJ/m ² or more even when the amount of the flame retardant added is increased.

The present invention can also be embodied as a lead-acid battery comprising a battery can according to the present invention, or a resin material for a battery can according to the present invention.

The construction of a lead-acid battery according to an embodiment of the present invention will hereinafter be described in detail.

A lead-acid battery according to an embodiment of the present invention includes a battery case including a case and a cover member, and a positive electrode, a negative electrode, a separator, and an electrolyte housed in the battery case.

<battery case>

The battery case includes a case having an opening at one end portion, and a cover member covering the opening of the case. An electrode group including a positive electrode and a negative electrode stacked via a separator and an electrolyte system impregnated with the electrode group are housed in the battery can. The battery case is formed of an ABS resin material.

In order to achieve good formability and reduce void space during transfer, the housing is preferably in the shape of a cube or a rectangular parallelepiped. However, as long as the casing has an opening at one end portion, the shape of the casing is not particularly limited, and the casing may have a different shape such as a polygonal column shape. The cover member is constructed of the same material as the housing and covers an opening of one end portion of the housing.

<Positive and Negative>

The positive electrode and the negative electrode have an active material held on a grid substrate. A paste-type electrode in which a paste-like active material is held on a cast grid substrate or an expanded grid substrate can be used as the positive electrode and the negative electrode. A Clad-type electrode prepared by inserting a mandrel made of a lead alloy into a braided glass fiber tube and filling the tube with an active material may also be used as the positive electrode.

The grid substrate contains lead as a main component and may contain tin, calcium, barium or the like. In particular, the gate substrate preferably contains calcium and tin. add Calcium addition reduces the rate of self-discharge. However, current collectors can corrode when calcium is added. Therefore, tin can be added to suppress the corrosion tendency of the current collector.

Paste electrodes can be made easier than coated electrodes. The paste-like active material can be kneaded by lead powder containing lead oxide, water, sulfuric acid, etc. (according to the properties of the positive electrode and the negative electrode, sometimes there are additives such as cut fiber, carbon powder, lignin, sulfuric acid钡, and lead dan) to manufacture. However, the preparation of the paste active material is not particularly limited.

<separator>

A separator is interposed between the positive electrode and the negative electrode to prevent short circuit between the positive electrode and the negative electrode. Specific examples of the separator include a porous sheet made of a blended fabric of fibers made of a material such as polyethylene, glass non-woven fabric, and polypropylene, and the like. However, the separator is not particularly limited.

<electrolyte>

The electrolyte can be prepared, for example, by diluting dilute sulfuric acid with pure water to a mass percentage concentration of about 30%, and then adjusting the concentration to an appropriate value in consideration of the capacity, life, and the like of the battery. Additives such as magnesium sulfate and silicone can be added depending on the desired properties of the lead-acid battery.

<lead-acid battery>

The paste active material is held on a gate substrate made of lead or lead alloy The past paste positive and negative electrodes are alternately stacked via separators. The strap is welded to the lug portion of the same polarity. In this way, an electrode group is fabricated. The electrode group is then disposed in the housing and the cover member is attached to the housing. Thereafter, the electrolyte was poured into the battery can to obtain an unformed lead-acid battery, and then the lead-acid battery was completed. The present invention is also applicable to a lead-acid battery using a coated electrode manufactured by filling a clad tube with lead powder.

[Examples]

Next, examples and comparative examples of the present invention will be described. The invention is not limited to the embodiments described below.

Techno ABS 150 manufactured by Techno Polymer Co., Ltd. was used as the ABS resin. FG-8500 manufactured by Teijin Ltd. was used as brominated bisphenol A. Antimony Trioxide M manufactured by Nihon Seiko Co., Ltd. was used as antimony trioxide. Bisamide LA manufactured by Nippon Kasei Chemical Co., Ltd. was used as (methylene-) bis-stearylamine.

<Example 1>

20 parts by mass of brominated bisphenol A (hereinafter also referred to as "brominated BPA") and 5 parts by mass of antimony trioxide per 100 parts by mass of the ABS resin having a haw impact value of 20 kJ/m ² (Sb ₂ O ₃ ) and 0.3 parts by mass of bis-stearylamine (hereinafter also referred to as "BSA") are added to the resin material. This resin material was kneaded (mixed) using an extruder sold by Ikegai Corp. as PCM 30 to form nine pellets. The pellets were processed using a large injection molding machine IS850GTW manufactured by Toshiba Machine Co., Ltd. to manufacture a housing having an outer dimension of 170 mm (vertical), 106 mm (horizontal), and 312 mm (height) and a thickness of 5.0 mm. . "Pi sand impact value of 20kJ / m ABS resin ² of" is meant a speech Pi in the sand under the impact value at room temperature after 20kJ / m ABS resin molding of ^2.

The electrode group is prepared by alternately stacking the positive and negative electrodes via a separator and welding a strap to a lug portion of the same polarity, and is disposed in the fabricated battery can. A lead-acid battery is prepared by mounting a lid member on a casing, pouring an electrolyte into the battery can, and forming a lead-acid battery. The lead-acid battery manufactured was tested for flammability and the value of the sand impact was measured according to the UL94 standard.

The test piece conforming to JIS K 7111-1 was prepared by cutting and forming a prescribed notch, and using a digital impact tester DG- manufactured by Toyo Seiki Seisaku-sho, Ltd. at 25 ° C in the atmosphere. UB to measure the impact value of the sand.

The processability of the fabricated battery can is evaluated based on the viewpoint of mold releasability and dimensional stability. The release property means whether the manufactured battery can be removed/disengaged from the mold without load. The dimensional stability indicates whether the battery case detached from the mold after forming is deformed when cooled to room temperature.

<Examples 2 and 3 and Comparative Examples 1 to 3>

A lead-acid battery was fabricated in the same manner as in Example 1, except for the three oxygen The addition amount of the diterpene was changed to 1, 3, 4, 7, and 10 parts by mass, and the obtained lead-acid battery was subjected to the same test and measurement as in Example 1.

The test results and measurement results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. In the "UL94V-0" column of the table, "NG" indicates that the flammability rating of UL94V-0 is not met, and "OK" indicates that the flammability rating of UL94V-0 is met.

The value in the "SP Shock" column indicates the measurement of the sand impact value. In the "Comprehensive Assessment" column, "NG" indicates that the flammability rating of UL94V-0 is not met and/or the sand impact value is less than 10kJ/m ² , and "OK" means that the flammability rating of UL94V-0 is met and sand. The 丕 impact value is 10 kJ/m ² or higher.

In the "Processability" column, "o" indicates that the battery case to be manufactured can be removed/disengaged from the mold without load and the battery case detached from the mold is not deformed after cooling to room temperature after molding, and "x" The battery case indicating that the manufactured battery case cannot be removed/disengaged from the mold under no load and/or detached from the mold is deformed after cooling to room temperature after forming.

In Examples 1 to 3 in which the amount of antimony trioxide added was 5 parts by mass or more, as shown in Table 1, the battery case manufactured conformed to the flammability rating of UL94V-0, and the impact value of the sand blast was 10 kJ/ m ² or higher and provides good processability. In Comparative Examples 1 to 3 in which the amount of antimony trioxide added was less than 5 parts by mass, the manufactured battery case had a higher haze impact value than Examples 1 to 3 and provided good workability, but did not conform to UL94V-0. The flammability rating.

<Comparative Examples 4 to 8>

The lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 13 parts by mass as shown in Table 2, and the obtained lead-acid battery was obtained. The same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were carried out.

In all of Comparative Examples 4 to 8 in which the amount of brominated bisphenol A added was less than 15 parts by mass as shown in Table 2, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good. Processability, but does not meet the flammability rating of UL94V-0.

<Examples 4 to 15 and Comparative Examples 9 to 16>

The lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 15 parts by mass, 17 parts by mass, and 23, respectively, as shown in Tables 3 to 6. The mass fraction and 25 parts by mass were subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2 for the obtained lead-acid battery.

In Examples 4 to 15 in which the amount of antimony trioxide added was 5 parts by mass or more, as shown in Tables 3 to 6, the battery case manufactured conformed to the flammability rating of UL94V-0, and the sand impact value was 10kJ/m ² or higher and provides good processability.

In Comparative Examples 9 to 16 in which the amount of antimony trioxide added was less than 5 parts by mass, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability, but did not conform to UL94V- 0 flammability rating.

<Comparative Examples 17 to 21>

The lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 27 parts by mass as shown in Table 7, and the obtained lead-acid battery was obtained. The same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were carried out.

In Comparative Examples 17 and 18 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Table 7, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability. However, it does not meet the flammability rating of UL94V-0.

In Comparative Examples 19 to 21 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case produced satisfies the flammability rating of UL94V-0 and provides good workability, but the sand blast impact value is lower than 10 kJ. /m ² .

Next, the ABS resin, which is a main component of the resin material, was changed to an ABS resin having a haw impact value of 15 kJ/m ² , and the lead-acid battery manufactured was subjected to a flammability test and a sand blast impact value according to the UL94 standard. . "Pi sand impact value of 15kJ / m ABS resin ² of" is meant a speech Pi in the sand under the impact value at room temperature after 15kJ / m ABS resin molding of ^2.

<Comparative Examples 22 to 27>

A lead-acid battery was produced in the same manner as in Comparative Examples 1 to 3 and Examples 1 to 3 except that the ABS resin was changed to an ABS resin having a haw impact value of 15 kJ/m ² as shown in Table 8, and the obtained lead was obtained. - The acid battery was subjected to the same tests and measurements as in Comparative Examples 1 to 3 and Examples 1 to 3.

In Comparative Examples 22 to 24 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Table 8, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability. However, it does not meet the flammability rating of UL94V-0.

In Comparative Examples 25 to 27 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case manufactured conformed to the flammability rating of UL94V-0 and provided good workability, but the sand blast impact value was less than 10 kJ. /m ² .

<Comparative Examples 28 to 32>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the ABS resin was changed to an ABS resin having a haw impact value of 15 kJ/m ² as shown in Table 9, and the obtained lead was obtained. - The acid battery was subjected to the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2.

In all of Comparative Examples 28 to 32, as shown in Table 9, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability, but did not meet the flammability rating of UL94 V-0.

<Comparative Examples 33 to 57>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that as shown in Tables 10 to 14, the ABS resin was changed to an ABS resin having a haw impact value of 15 kJ/m ² and bromine. The addition of bisphenol A was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass, and 27 parts by mass, respectively, and the obtained lead-acid batteries were compared with Examples 1 to 3 and Comparative Example 1 and 2 same test and measurement.

In Comparative Examples 33, 34, 38, 39, 43, and 44 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Tables 10 to 14, the battery shell produced had a hail impact value of 10 kJ/ m ² or higher and provides good processability, but does not meet the flammability rating of UL94V-0.

In Comparative Examples 35 to 37, 40 to 42, 45 to 47, 50 to 52, and 55 to 57 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case manufactured conformed to UL94V-0. A flammability rating and good processability, but a haw impact value of less than 10 kJ/m ² .

In Comparative Examples 48, 49, 53 and 54 in which the amount of antimony trioxide added was less than 5 parts by mass, the battery case produced provided good workability, but the hail impact value was less than 10 kJ/m ² and did not conform to UL94V-0 flammability rating.

Next, the ABS resin, which is a main component of the resin material, was changed to an ABS resin having a hail impact value of 10 kJ/m ² , and the lead-acid battery manufactured was subjected to a flammability test and a sand blast impact value according to the UL94 standard. . "Pi sand impact value of 10kJ / m ABS resin ² of" is meant a speech Pi in the sand under the impact value at room temperature after 10kJ / m ABS resin molding of ^2.

<Comparative Examples 58 to 63>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3 except that the ABS resin was changed to an ABS resin having a Satay impact value of 10 kJ/m ² as shown in Table 15, and the lead obtained was obtained. - The acid battery was subjected to the same tests and measurements as in Comparative Examples 1 to 3 and Examples 1 to 3.

In Comparative Examples 58 to 60 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Table 15, the battery case produced provided good workability, but the hail impact value was less than 10 kJ/m ² , and Meets the flammability rating of UL94V-0.

In Comparative Examples 61 to 63 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case manufactured satisfies the flammability rating of UL94V-0 and provides good workability, but the sand blast impact value is lower than 10 kJ. /m ² .

<Comparative Examples 64 to 68>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the ABS resin was changed to an ABS resin having a haw impact value of 10 kJ/m ² as shown in Table 16, and the lead obtained was obtained. - The acid battery was subjected to the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2.

In all of Comparative Examples 64 to 68, as shown in Table 16, the fabricated battery can provided good workability, but the sand impact value was less than 10 kJ/m ² and did not meet the UL94 V-0 flammability rating.

<Comparative Examples 69 to 93>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that as shown in Tables 17 to 21, the ABS resin was changed to an ABS resin having a haw impact value of 10 kJ/m ² and bromine. The amount of bisphenol A added was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass, and 27 parts by mass, respectively, and the obtained lead-acid batteries were subjected to Examples 1 to 3 and Comparative Example 1. And 2 the same test and measurement.

The battery case manufactured in Comparative Examples 69, 70, 74, 75, 79, 80, 84, 85, 89, and 90 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Tables 17 to 21 Provides good processability, but does not meet the flammability rating of UL94V-0 and the sand impact value is less than 10kJ/m ² .

In Comparative Examples 71 to 73, 76 to 78, 81 to 83, 86 to 88, and 91 to 93 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case manufactured conformed to UL94V-0. A flammability rating and good processability, but a haw impact value of less than 10 kJ/m ² .

Next, the ABS resin, which is a main component of the resin material, was changed to an ABS resin having a hail impact value of 25 kJ/m ² , and the lead-acid battery manufactured was subjected to a flammability test and a sand blast impact value according to the UL94 standard. . "Pi sand impact value of 25kJ / m ABS resin ² of" is meant a speech Pi in the sand under the impact value at room temperature after 25kJ / m ABS resin molding of ^2.

<Examples 16 to 18 and Comparative Examples 94 to 96>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3 except that the ABS resin was changed to an ABS resin having a haw impact value of 25 kJ/m ² as shown in Table 22, and the obtained lead was obtained. - The acid battery was subjected to the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 to 3.

In Examples 16 to 18 in which the amount of antimony trioxide added was 5 parts by mass or more, as shown in Table 22, the battery case manufactured conformed to the flammability rating of UL94V-0, and the impact value of the sand blast was 10 kJ/ m ² or higher and provides good processability. In Comparative Examples 94 to 96 in which the amount of antimony trioxide added was less than 5 parts by mass, the cell shell produced had a higher haze impact value than Examples 16 to 18 and provided good processability, but did not conform to UL94V-0. The flammability rating.

<Comparative Examples 97 to 101>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the ABS resin was changed to an ABS resin having a haw impact value of 25 kJ/m ² as shown in Table 23 and brominated bisphenol. The amount of addition of A was changed to 13 parts by mass, and the obtained lead-acid battery was subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2.

In all of Comparative Examples 97 to 101, as shown in Table 23, the battery case produced had a haw impact value of 10 kJ/m ² or more and provided good workability, but did not meet the flammability rating of UL94 V-0.

<Examples 19 to 30 and Comparative Examples 102 to 109>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that as shown in Tables 24 to 27, the ABS resin was changed to an ABS resin having a haw impact value of 25 kJ/m ² and bromine. The amount of bisphenol A added was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, and 25 parts by mass, respectively, and the obtained lead-acid battery was subjected to the same conditions as those of Examples 1 to 3 and Comparative Examples 1 and 2. Test and measurement.

In Examples 19 to 30 in which the amount of antimony trioxide added was 5 parts by mass or more, as shown in Tables 24 to 27, the battery case manufactured conformed to the flammability rating of UL94V-0, and the impact value of the sand was 10kJ/m ² or higher and provides good processability.

In Comparative Examples 102 to 109 in which the amount of antimony trioxide added was less than 5 parts by mass, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability, but did not conform to UL94 V-0. The flammability rating.

<Comparative Examples 110 to 114>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the ABS resin was changed to an ABS resin having a haw impact value of 25 kJ/m ² as shown in Table 28 and brominated bisphenol. The amount of addition of A was changed to 27 parts by mass, and the obtained lead-acid battery was subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2.

In Comparative Examples 110 and 111 in which the amount of addition of antimony trioxide was less than 5 parts by mass as shown in Table 28, the battery case produced had a hail impact value of 10 kJ/m ² or more and provided good workability. However, it does not meet the flammability rating of UL94V-0.

In Comparative Examples 112 to 114 in which the amount of antimony trioxide added was 5 parts by mass or more, the battery case manufactured conformed to the flammability rating of UL94V-0 and provided good workability, but the sand blast impact value was less than 10 kJ. /m ² .

Next, the amount of the addition of distearylamine is changed to 0 parts by mass (without addition of distearylamine), 0.1 parts by mass, 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the lead-acid obtained is obtained. The battery is tested.

<Examples 31 to 42 and Comparative Examples 115 to 117>

A lead-acid battery was produced in the same manner as in Examples 1 to 3 except that the amount of the addition of the bis-stearylamine was changed to 0 parts by mass as shown in Tables 29 to 31 (no addition of distearylamine), 0.1 part by mass. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 1 to 3.

In Comparative Examples 115 to 117 in which no distearylamine was added as shown in Tables 29 to 31, the produced battery can meet the flammability rating of UL94V-0 and the hail impact value was 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 31 to 42 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the sand impact value is 10 kJ/m ² or more, and provides good processability.

<Examples 43 to 54 and Comparative Examples 118 to 120>

A lead-acid battery was produced in the same manner as in Examples 4 to 6, except that the addition amount of distearylamine was changed to 0 parts by mass (without addition of distearylamine) and 0.1 part by mass as shown in Tables 32 to 34. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 4 to 6.

In Comparative Examples 118 to 120 in which no distearylamine was added as shown in Tables 32 to 34, the produced battery can meet the flammability rating of UL94V-0 and the hail impact value was 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 43 to 54 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the hail impact value is 10 kJ/m ² or more, and provides good processability.

<Examples 55 to 66 and Comparative Examples 121 to 123>

A lead-acid battery was produced in the same manner as in Examples 13 to 15, except that the addition amount of distearylamine was changed to 0 parts by mass as shown in Tables 35 to 37 (without addition of distearylamine) and 0.1 part by mass. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 13 to 15.

In Comparative Examples 121 to 123 in which no distearylamine was added as shown in Tables 35 to 37, the produced battery can meet the flammability rating of UL94V-0 and the hail impact value was 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 55 to 66 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the hail impact value is 10 kJ/m ² or more, and provides good processability.

<Examples 67 to 78 and Comparative Examples 124 to 126>

A lead-acid battery was produced in the same manner as in Examples 16 to 18 except that the addition amount of distearylamine was changed to 0 parts by mass as shown in Tables 38 to 40 (without addition of distearylamine) and 0.1 part by mass. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 16 to 18.

In Comparative Examples 124 to 126 in which no distearylamine was added as shown in Tables 38 to 40, the battery can be manufactured to meet the flammability rating of UL94V-0 and the hail impact value is 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 67 to 78 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the hail impact value is 10 kJ/m ² or more, and provides good processability.

<Examples 79 to 90 and Comparative Examples 127 to 129>

A lead-acid battery was produced in the same manner as in Examples 19 to 21 except that the addition amount of distearylamine was changed to 0 parts by mass as shown in Tables 41 to 43 (without addition of distearylamine) and 0.1 part by mass. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 19 to 21.

In Comparative Examples 127 to 129 in which no distearylamine was added as shown in Tables 41 to 43, the battery can be manufactured to meet the flammability rating of UL94V-0 and the hail impact value is 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 79 to 90 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the hail impact value is 10 kJ/m ² or more, and provides good processability.

<Examples 91 to 102 and Comparative Examples 130 to 132>

A lead-acid battery was produced in the same manner as in Examples 28 to 30 except that the addition amount of bis-stearamide was changed to 0 parts by mass as shown in Tables 44 to 46 (without addition of distearylamine) and 0.1 part by mass. 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 28 to 30.

In Comparative Examples 130 to 132 in which no distearylamine was added as shown in Tables 44 to 46, the produced battery can meet the flammability rating of UL94V-0 and the hail impact value was 10 kJ/m ² or more. However, it does not provide good processability.

In Examples 91 to 102 in which distearylamine was added, the battery can be manufactured to meet the flammability rating of UL94V-0, the hail impact value is 10 kJ/m ² or more, and provides good processability.

According to the present invention, a battery case for a lead-acid battery is formed of a resin material containing an ABS resin having a hail impact value of 20 kJ/m ² or more (as a main component) and a flame retardant added thereto. . Thus, a battery case for a lead-acid battery which is highly resistant to ignition at a flammability rating of UL94V-0 and has a sand blast impact value of 10 kJ/m ² or higher can be obtained.

Although certain features of the invention have been described with reference to example embodiments, the description Various modifications of the example embodiments, as well as other embodiments of the invention, which are obvious to those skilled in the art of the invention, are considered to be within the spirit and scope of the invention.

Claims (10)

A battery case for a lead-acid battery, which comprises an ABS resin having a Charpy impact value of 20 kJ/m ² or more as a main component and a resin material containing an additive of a flame retardant Molded, wherein the additive contains 15 to 25 parts by mass of brominated bisphenol A, 5 parts by mass or more of antimony trioxide, and 0.1 part by mass or more per 100 parts by mass of the ABS resin. The bis-stearic acid amide is such that the battery case conforms to the flammability class of UL94V-0 and the cell shell has a hail impact value of 10 kJ/m ² or higher. A battery case for a lead-acid battery, which is molded from a resin material including an ABS resin having a haw impact value of 20 kJ/m ² or more as a main component and an additive containing a flame retardant, wherein The additive is added to the resin material such that the battery can meet the flammability rating of UL94V-0 and the cell shell has a hail impact value of 10 kJ/m ² or higher. A battery case for a lead-acid battery according to claim 2, wherein the additive contains brominated bisphenol A, antimony trioxide, and fatty acid amide. A battery case for a lead-acid battery according to item 3 of the patent application, wherein the additive contains 15 to 25 masses per 100 parts by mass of the ABS resin having a haw impact value of 20 kJ/m ² or more. The brominated bisphenol A, 5 parts by mass or more of antimony trioxide, and 0.1 part by mass or more of fatty decylamine. A battery case for a lead-acid battery according to item 4 of the patent application, wherein the fatty guanamine is bis-stearamine. A battery case for a lead-acid battery according to claim 2, wherein the ABS resin as a main component of the resin material has a haw impact value of 25 kJ/m ² or more. A lead-acid battery comprising the battery case for a lead-acid battery according to any one of claims 1 to 6. A resin material for a battery case of a lead-acid battery, comprising: an ABS resin having a hail impact value of 20 kJ/m ² or more; and a BBS containing brominated bisphenol A and trioxide added to the ABS resin An additive for bismuth and fatty guanamine. The resin material for a battery case of a lead-acid battery according to claim 8, wherein the additive added to the resin material contains 15 to 25 parts by mass of bromine per 100 parts by mass of the ABS resin. Bisphenol A, 5 parts by mass or more of antimony trioxide, and 0.1 part by mass or more of fatty decylamine. A battery for a lead-acid battery as claimed in claim 9 A resin material of a shell in which the fatty amide is distearylamine.