JP6303651B2 - Lead-acid battery battery, lead-acid battery using lead-acid battery battery, and resin composition of lead-acid battery battery - Google Patents

Description

  The present invention relates to a battery for lead-acid batteries, a lead-acid battery using a battery for lead-acid batteries, and a resin composition for a battery for lead-acid batteries, more specifically, a battery for a control valve type lead-acid battery, It is related with the resin composition of the lead storage battery which uses the battery case for control valve type lead acid batteries, and the battery case for control valve type lead acid batteries.

  Control valve-type lead-acid batteries take advantage of features such as maintenance-free, almost no acid mist, and no gas emission, and are used for large-sized stationary batteries, including uninterruptible power supplies such as portable devices, cordless devices, and computer backup power supplies. It is also used as a main power source for electric vehicles and for starting automobile engines. It is also used as an industrial battery for emergency power supplies in office buildings, hospitals, etc., power load leveling (peak cut, peak shift) power storage systems, and output stabilizers for natural energy generators.

  In addition, the demand for lead-acid batteries is increasing year by year because they are more economical than other secondary batteries and have stable performance. The required characteristics of batteries are diversifying due to wide range and light weight, and the required quality level is increasing year by year.

  A lead storage battery performs charge and discharge by a chemical reaction between an electrode group disposed in a battery case and dilute sulfuric acid as an electrolytic solution. Since dilute sulfuric acid is strongly acidic and there is a danger to leakage of the electrolyte, it is necessary to pay sufficient attention to damage, cracking and deterioration of the battery case. Therefore, high acid resistance and sulfuric acid resistance are required for the battery case of the lead storage battery.

  If the battery case is broken or cracked, the electrolyte may leak and damage peripheral equipment.

  Furthermore, the battery case of the lead storage battery is required to have impact resistance, mechanical strength and flame retardancy from the viewpoint of disaster prevention (fire prevention), and high formability.

  JP 2002-42748 A (Patent Document 1) discloses a battery case made of flame-retardant polypropylene. Japanese Patent Laying-Open No. 2006-348098 (Patent Document 2) discloses a lead-acid battery casing made of a polycarbonate-based resin having mechanical strength, moldability, and flame retardancy. In addition, in Japanese translations of PCT publication No. 2008-519153 (Patent Document 3), if it contains a bromine-based organic compound flame retardant, an antimony-based flame retardant auxiliary agent, and a stearamide-based compound, only flame retardant is excellent. In particular, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) composition having significantly improved weather resistance and thermal stability and improved workability by increasing impact strength and fluidity is disclosed.

JP 2002-42748 A JP 2006-348098 A Special table 2008-519153 gazette

  Lead-acid batteries installed in mobile phone base stations, etc. are used as emergency power when commercial power is lost due to disasters, etc. Reliability to operate is required. Especially in areas with poor transportation, it is difficult to perform maintenance of lead-acid batteries frequently, so long-term safety and reliability are required, and some abnormalities have occurred in the power supply system or lead-acid batteries, leading to fires. Sometimes it is important not to spread to peripheral equipment. Therefore, it is requested | required that the resin material of combustibility class UL94-V0 which has a self-extinguishing property also to the battery case of a lead storage battery.

  In addition, the lead storage battery battery case may become fouled, dented, or the like during transportation of the lead storage battery and installation at a predetermined place, or due to handling when performing maintenance of the storage battery. In addition, the battery case of the lead storage battery expands and contracts with the installation ambient temperature that varies depending on the season in the morning and evening, causing stress and concentration on the ridges and dents, resulting in damage, cracks, etc. There is. A lead-acid battery used as an emergency power supply is normally in a fully charged standby state in preparation for an emergency. Check the capacity of the lead-acid battery and investigate whether there is a malfunction in the lead-acid battery. For this reason, inspection may be performed by discharging the battery at regular intervals. After the inspection, the battery is fully charged and the capacity is restored to return to the standby state. However, the lead storage battery generates heat due to the charge and discharge during the inspection, and the battery case may expand and contract, causing the battery case to break or crack. .

  It is conceivable that leakage current and spark are generated through the electrolyte solution leaked from the damaged portion of the battery case, and the lead storage battery and peripheral devices are damaged. Furthermore, when a short circuit occurs between the battery case and the lead-acid battery storage device through the damaged part of the battery case, the lead-acid battery becomes hot, and the battery case and peripheral devices may ignite and spread to the surroundings. For this reason, a battery case having excellent impact resistance is required so that the battery case is not subject to wrinkles, dents, or the like even if sufficient care is not taken in the transportation and maintenance of lead-acid batteries.

  Some ABS resins have high impact properties. However, an ABS resin having high impact resistance has low fluidity, and thus processability is lowered. Therefore, when the battery case for the lead storage battery is formed of ABS resin, there is a problem that only ABS resin having low impact resistance can be used in order to maintain processability. Moreover, if a flame retardant is added to impart flame retardancy to the ABS resin, the impact resistance of the ABS resin is further lowered. Therefore, the conventional ABS resin-based resin composition cannot sufficiently enhance the flame retardancy and impact resistance of the battery case of the lead storage battery.

  An object of the present invention is to provide a battery case for an ABS resin-based lead storage battery, which has excellent impact resistance even if the processability and flame retardancy are sufficiently enhanced, a lead storage battery using a lead storage battery, and a lead storage battery. It is providing the resin composition of a battery case.

In order to solve the above-mentioned problems, the inventors have intensively studied and examined. As a result, if the resin material is mainly composed of ABS resin having a Charpy impact value of 20 kJ / m ² or more, the flammability class is UL94V-0. It has been found that even when a flame retardant is added so as to satisfy the standard, a battery case for a lead storage battery having a Charpy impact value of 10 kJ / m ² or more can be obtained. Based on this finding, the inventors conducted research to use an aliphatic amide in combination with a brominated bisphenol A as a flame retardant and antimony trioxide as a flame retardant aid in order to improve the workability of the resin material. It was. In addition, a study was conducted on the addition of brominated bisphenol A as a flame retardant and antimony trioxide as a flame retardant auxiliary when the main component is an ABS resin having a Charpy impact value of 20 kJ / m ² or more. As a result, the battery case for the lead storage battery has good processability during molding, the flammability class satisfies the UL94V-0 standard, the Charpy impact value is 10 kJ / m ² or more, and the sulfuric acid resistance and It has been found that a battery case for a lead storage battery having high oxidation resistance can be obtained. The present invention is based on the above findings.

The object of the present invention is to improve a battery case for a lead-acid battery formed of a resin material containing an ABS resin as a main component and added with an additive containing a flame retardant. In the present invention, by using an ABS resin having a Charpy impact value of 20 kJ / m ² or more as a main component, an additive containing a flame retardant is provided so that high flame resistance satisfying a flammability class of UL94V-0 can be obtained. Even if an agent is added, a battery case for a lead storage battery having a Charpy impact value of 10 kJ / m ² or more and having high workability can be obtained.

  Here, the UL94 standard is a standard number for the flammability test of plastic materials for parts of equipment of UL (Underwriters Laboratories Inc.) in the United States, which has an international influence as a safety standard.

  The Charpy impact value is a value measured in an atmosphere at 25 ° C. according to JIS K7111-1. Specifically, the energy required for breaking the sample is divided by the cross-sectional area before breaking the sample. The higher this value, the better the toughness and the harder it is to break.

  As a specific resin material, for example, brominated bisphenol A, antimony trioxide and fatty acid amide can be added as additives. The combination of brominated bisphenol A, antimony trioxide and fatty acid amide is a combination of additives that can sufficiently enhance both impact resistance, processability and flame retardancy.

  In this specification, fatty acid amide means stearic acid amide, stearic acid bisamide, hydroxy stearic acid bisamide, m-xylylene bis stearic acid amide, N, N′-distearylisophthalic acid amide, N, N′-distearyl sebacin Acid amide, N, N′-distearyladipic acid amide, butylene bishydroxystearic acid amide, hexamethylene bishydroxystearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, ethylene bisbehenic acid amide , Ethylene bishydroxystearic acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, ethylene biscapric acid amide, ethylene biscaprylic acid amide, methylene bishydroxystearic acid amide Methylene bis lauric acid amide, is intended to include methylene bis-stearic acid amide.

As a specific composition of the resin material, 15 to 25 parts by mass of brominated bisphenol A, 5 parts by mass or more of antimony trioxide and 100 parts by mass of ABS resin having a Charpy impact value of 20 kJ / m ² or more and The additive which adjusted aliphatic amide to 0.1 mass part or more can be added.

  The fatty acid amide can be, for example, stearic acid bisamide (SBA).

The ABS resin which is the main component of the resin material is preferably an ABS resin having a Charpy impact value of 25 kJ / m ² or more. If it does in this way, even if it increases the addition amount of a flame retardant, the Charpy impact value of the battery case for lead acid batteries can be reliably made into 10 kJ / m < ² > or more.

  This invention can also be grasped | ascertained as the resin material for the lead storage battery provided with the battery case for lead acid batteries of this invention, or the battery case for lead acid batteries of this invention.

  Hereinafter, the configuration of the embodiment of the lead storage battery of the present invention will be described in detail.

  The lead storage battery according to the embodiment of the present invention includes a battery case including a battery case body and a lid, and a positive electrode plate, a negative electrode plate, a separator, and an electrolyte solution housed in the battery case.

<Battery>
The battery case includes a battery case body having one end opened, and a lid that covers the opening of the battery case body. Inside the battery case, an electrode group having a positive electrode plate and a negative electrode plate stacked via a separator and an electrolyte solution in which the electrode group is immersed are accommodated. The battery case is made of an ABS resin material.

  The battery case body preferably has a cubic or rectangular parallelepiped shape because the moldability and the ineffective space during conveyance can be reduced. However, as long as one end is open, the shape is not particularly limited, and other shapes such as a polygonal column can be used. The lid is made of the same material as the battery case main body and covers the opening at one end of the battery case main body.

<Positive electrode plate / Negative electrode plate>
The positive electrode plate and the negative electrode plate are obtained by holding an active material on a lattice substrate, and a paste-type electrode plate in which a pasty active material is held on a cast lattice substrate or an expanded lattice substrate can be used. Alternatively, a clad electrode plate may be used in which a lead alloy core is passed through a tube made of glass fiber and filled with an active material and used mainly as a positive electrode plate.

  The lattice substrate is made of lead as a main raw material, and tin, calcium, antimony, and the like can be added thereto. In particular, calcium and tin are preferably used. Although the proportion of self-discharge can be reduced by adding calcium, the ease of corrosion of the current collector, which is a problem at that time, can be suppressed by adding tin.

  Paste electrode plates can be manufactured more easily than clad electrode plates. For example, lead powder containing lead monoxide, water, sulfuric acid, etc. (additives such as cut fiber, carbon powder, lignin, barium sulfate, lead red, etc. according to the characteristics of the positive electrode and negative electrode) May be added), but is not particularly limited.

<Separator>
The separator is interposed between the positive electrode plate and the negative electrode plate, and prevents a short circuit between the positive electrode and the negative electrode. Specific examples of the separator may include a porous sheet made of a material such as polyethylene, glass nonwoven fabric, and polypropylene, and a mixed fabric of fibers made of these materials, but are not particularly limited.

<Electrolyte>
For example, an electrolyte prepared by diluting dilute sulfuric acid with purified water and preparing a concentration of about 30% by mass in terms of mass percent concentration can be adjusted to an appropriate concentration in consideration of battery capacity, life and the like. In addition, you may add additives, such as magnesium sulfate and a silica gel, according to the characteristic requested | required of a lead storage battery.

<Lead battery>
The lead-acid battery of the present invention is formed by alternately laminating paste-type positive and negative plates holding a paste-like active material on a grid substrate made of lead or a lead alloy via separators, and welding straps to the same polarity ears. Thus, an electrode plate group was produced. The electrode plate group can be prepared by placing it in the battery case body, attaching a lid, injecting an electrolyte into the battery case, and then forming it. Further, the present invention can also be applied to a lead-acid battery using a clad electrode plate manufactured by filling a clad tube with lead powder.

  Next, examples and comparative examples of the present invention will be described. In addition, this invention is not restrict | limited to the following Example.

  Techno ABS 150 from Techno Polymer Co., Ltd. as ABS resin, FG-8500 from Teijin Chemicals Ltd. as brominated bisphenol A, Antimony trioxide M from Nippon Seiko Co., Ltd. as antimony trioxide, (methylene) stearic acid Bisamide LA manufactured by Nippon Kasei Co., Ltd. was used as a bisamide.

<Example 1>
A resin material obtained by adding 20 parts by mass of brominated bisphenol A, 5 parts by mass of antimony trioxide, and 0.3 parts by mass of stearic acid bisamide to 100 parts by mass of ABS resin having a Charpy impact value of 20 kJ / m ^2. A pellet was formed by compounding (mixing) using an extruder sold by Ikegai Co., Ltd. under the name PCM30. Using this pellet, a large-sized injection molding machine IS850GTW manufactured by TOSHIBA MACHINE Co., Ltd. was used to produce a battery case main body having an outer dimension of 170 mm × width: 106 mm × height: 312 mm and a thickness of 5.0 mm. Here, the "Charpy impact value ABS resin becomes 20 kJ / ^{m 2",} Charpy impact value in the state which became to room temperature after molding means ABS resin becomes 20 kJ / ^{m 2.}

  In the produced battery case, positive and negative electrode plates are alternately laminated via separators, and a group of electrode plates in which straps are welded to the same polarity ears are arranged, and the lid is attached to the inside of the battery case. A lead-acid battery was produced by injecting an electrolytic solution and performing chemical conversion. About the produced lead acid battery, the UL94 flammability test and the measurement of the Charpy impact value were performed.

  In addition, the Charpy impact test cuts out a test piece based on JIS K7111-1 and performs a specified notch process, and uses a digital impact tester DG-UB type manufactured by Toyo Seiki Seisakusho Co., Ltd. at 25 ° C. in an ambient temperature. It was measured.

  Moreover, the workability of the produced battery case was evaluated from releasability and dimensional stability. The releasability indicates whether or not the produced battery case can be removed / released from the mold without load, and the dimensional stability indicates whether or not the released battery case is deformed during cooling to room temperature. Indicate.

<Examples 2-3 and Comparative Examples 1-3>
A lead storage battery was produced in the same manner as in Example 1 except that the amount of antimony trioxide added was changed to 1, 3, 4, 7, and 10 parts by mass, and the same tests and measurements as in Example 1 were performed.

  The test results and measurement results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. In the table, “NG” in the “UL94V0” column indicates that the combustibility class does not satisfy UL94V-0, and “OK” indicates that the combustibility class satisfies UL94V-0.

The numerical value in the “SP impact” column indicates the measurement result of the Charpy impact value. “NG” in the “Comprehensive evaluation” column indicates that the flammability class does not satisfy UL94V-0 and / or the Charpy impact value is less than 10 kJ / m ² , and “OK” indicates that the flammability class is UL94V. 0 is satisfied, and the Charpy impact value is 10 kJ / m ² or more.

Furthermore, “◯” in the column of “workability” indicates that the produced battery case can be removed / released from the mold without load, and the battery case released after molding does not deform during cooling to room temperature. , “X” indicates that the produced battery case could not be removed / released from the mold without load and / or the battery case released after molding was deformed during cooling to room temperature.

As shown in Table 1, in Examples 1 to 3 in which the addition amount of antimony trioxide is 5 parts by mass or more, the produced battery case has a combustibility class of UL94V-0 and a Charpy impact value of 10 kJ / m ² or more, and the workability was good. In Comparative Examples 1 to 3 in which the amount of antimony trioxide added is less than 5 parts by mass, the produced battery case had a Charpy impact value higher than those in Examples 1 to 3, and the workability was also good. The flammability class did not satisfy UL94V-0.

<Comparative Examples 4-8>
As shown in Table 2, lead acid batteries were prepared in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the amount of brominated bisphenol A added was changed to 13 parts by mass. And the same test and measurement as Comparative Examples 1 and 2 were performed.

As shown in Table 2, in any of Comparative Examples 4 to 8 in which the addition amount of brominated bisphenol A is less than 15 parts by mass, the produced battery case has a Charpy impact value of 10 kJ / m ² or more and workability. Was good, but the flammability class did not satisfy UL94V-0.

<Examples 4 to 15 and Comparative Examples 9 to 16>
As shown in Tables 3-6, Examples 1-3 and Comparative Examples 1-2, except that the addition amount of brominated bisphenol A was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, and 25 parts by mass. A lead storage battery was produced in the same manner as described above, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed.

As shown in Tables 3 to 6, in Examples 4 to 15 in which the addition amount of antimony trioxide is 5 parts by mass or more, the produced battery case has a combustibility class of UL94V-0 and a Charpy impact value. It was 10 kJ / m ² or more, and the workability was also good.

In Comparative Examples 9 to 16 in which the amount of antimony trioxide added is less than 5 parts by mass, the Charpy impact value was 10 kJ / m ² or more and the workability was good, but the produced battery case had a combustibility class. Did not satisfy UL94V-0.

<Comparative Examples 17-21>
As shown in Table 7, lead acid batteries were prepared in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the amount of brominated bisphenol A added was changed to 27 parts by mass. And the same test and measurement as Comparative Examples 1 and 2 were performed.

As shown in Table 7, in Comparative Examples 17 to 18 in which the amount of antimony trioxide added was less than 5 parts by mass, the Charpy impact value was 10 kJ / m ² or more, and the workability was good, but the fabrication was performed. The battery case did not satisfy UL94V-0 in the flammability class.

In Comparative Examples 19 to 21 in which the addition amount of antimony trioxide is 5 parts by mass or more, the produced battery case had a combustibility class of UL94V-0 and good workability, but had a Charpy impact value. It was less than 10 kJ / m ² .

Next, the ABS resin which is the main component of the resin material was changed to an ABS resin having a Charpy impact value of 15 kJ / m ² , and UL94 flammability test and measurement of Charpy impact value were performed. Here, the "Charpy impact value ABS resin becomes 15 kJ / ^{m 2",} Charpy impact value in the state which became to room temperature after molding means ABS resin becomes 15 kJ / ^{m 2.}

<Comparative Examples 22-27>
As shown in Table 8, lead acid batteries were prepared in the same manner as Comparative Examples 1 to 3 and Examples 1 to 3 except that the ABS resin was changed to an ABS resin having a Charpy impact value of 15 kJ / m ² . Tests and measurements similar to those of Comparative Examples 1 to 3 and Examples 1 to 3 were performed.

As shown in Table 8, in Comparative Examples 22 to 24 in which the addition amount of antimony trioxide is less than 5 parts by mass, the produced battery case has a Charpy impact value of 10 kJ / m ² or more, and the workability is good. However, the flammability class did not satisfy UL94V-0.

In Comparative Examples 25 to 27 in which the amount of antimony trioxide added is 5 or more, the combustibility class satisfies UL94V-0 and the workability is good, but the Charpy impact value is less than 10 kJ / m ² .

<Comparative Examples 28-32>
As shown in Table 9, Examples 1 to 3 and Comparative Example except that the ABS resin was changed to an ABS resin having a Charpy impact value of 15 kJ / m ² and the addition amount of brominated bisphenol A was changed to 13 parts by mass. Lead storage batteries were produced in the same manner as in Examples 1 and 2, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed.

As shown in Table 9, in each of Comparative Examples 28 to 32, the produced battery case had a Charpy impact value of 10 kJ / m ² or more and good workability, but the combustibility class was UL94V-0. I was not satisfied.

<Comparative Examples 33-57>
As shown in Tables 10 to 14, the ABS resin was changed to an ABS resin having a Charpy impact value of 15 kJ / m ^2, and the addition amount of brominated bisphenol A was 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass. The lead storage battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the parts were changed to parts and 27 parts by mass, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed. went.

As shown in Tables 10 to 14, in Comparative Examples 33 to 34, 38 to 39, and 43 to 44 in which the amount of antimony trioxide added is less than 5 parts by mass, the Charpy impact value is 10 kJ / m ² or more, and the workability is increased. However, the produced battery case did not satisfy UL94V-0 in the flammability class.

In Comparative Examples 35 to 37, 40 to 42, 45 to 47, 50 to 52, and 55 to 57 in which the addition amount of antimony trioxide is 5 parts by mass or more, the produced battery case has a flammability class of UL94V-0. Satisfactory and workability was good, but Charpy impact value was less than 10 kJ / m ² .

In Comparative Examples 48 to 49 and 53 to 54, the workability was good, but the Charpy impact value was less than 10 kJ / m ² , and the produced battery case did not satisfy UL94V-0 in the flammability class. .

Next, the ABS resin which is the main component of the resin material was changed to an ABS resin having a Charpy impact value of 10 kJ / m ² , and UL94 flammability test and measurement of Charpy impact value were performed. Here, the "Charpy impact value ABS resin becomes 10 kJ / ^{m 2",} Charpy impact value in the state which became to room temperature after molding means ABS resin becomes 10 kJ / ^{m 2.}

<Comparative Examples 58-63>
As shown in Table 15, a lead storage battery was produced in the same manner as Comparative Examples 1 to 3 and Examples 1 to 3, except that the ABS resin was changed to an ABS resin having a Charpy impact value of 10 kJ / m ² . Tests and measurements similar to those of Comparative Examples 1 to 3 and Examples 1 to 3 were performed.

As shown in Table 15, in Comparative Examples 58 to 60 in which the addition amount of antimony trioxide is less than 5 parts by mass, the produced battery case has good workability, but the Charpy impact value is less than 10 kJ / m ^2. The flammability class did not satisfy UL94V-0.

In Comparative Examples 61 to 63 in which the amount of antimony trioxide added is 5 parts by mass or more, the combustibility class satisfies UL94V-0 and the workability is good, but the Charpy impact value is less than 10 kJ / m ^2. It was.

<Comparative Examples 64-68>
As shown in Table 16, Examples 1 to 3 and Comparative Example except that the ABS resin was changed to an ABS resin having a Charpy impact value of 10 kJ / m ² and the addition amount of brominated bisphenol A was changed to 13 parts by mass. Lead storage batteries were produced in the same manner as in Examples 1 and 2, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed.

As shown in Table 16, in all of Comparative Examples 64-68, the workability was good, but the produced battery case had a Charpy impact value of less than 10 kJ / m ² and a combustibility class of UL94V-0. I was not satisfied.

<Comparative Examples 69-93>
As shown in Tables 17 to 21, the ABS resin was changed to an ABS resin having a Charpy impact value of 10 kJ / m ^2, and the addition amount of brominated bisphenol A was 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass. The lead storage battery was produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2 except that the parts were changed to parts and 27 parts by mass, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed. went.

As shown in Tables 17 to 21, in Comparative Examples 69 to 70, 74 to 75, 79 to 80, 84 to 85, and 89 to 90 in which the addition amount of antimony trioxide is less than 5 parts by mass, the workability is good. However, the produced battery case did not satisfy UL94V-0 in the flammability class, and the Charpy impact value was less than 10 kJ / 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 is 5 parts by mass or more, the produced battery case has a flammability class of UL94V-0. Satisfactory and workability was good, but Charpy impact value was less than 10 kJ / m ² .

Next, the ABS resin which is the main component of the resin material was changed to an ABS resin having a Charpy impact value of 25 kJ / m ² , and UL94 flammability test and measurement of Charpy impact value were performed. Here, the "Charpy impact value ABS resin becomes 25 kJ / ^{m 2",} Charpy impact value in the state which became to room temperature after molding means ABS resin becomes 25 kJ / ^{m 2.}

<Examples 16 to 18 and Comparative Examples 94 to 96>
As shown in Table 22, except that the ABS resin was changed to an ABS resin having a Charpy impact value of 25 kJ / m ² , lead acid batteries were produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3, Tests and measurements similar to those in Examples 1 to 3 and Comparative Examples 1 to 3 were performed.

As shown in Table 22, in Examples 16 to 18 in which the addition amount of antimony trioxide is 5 parts by mass or more, the produced battery case has a combustibility class of UL94V-0 and a Charpy impact value of 10 kJ / m ² or more, and the workability was good. In Comparative Examples 94 to 96 in which the addition amount of antimony trioxide is less than 5 parts by mass, the produced battery case had a Charpy impact value higher than those in Examples 16 to 18, and the workability was good. The flammability class did not satisfy UL94V-0.

<Comparative Examples 97-101>
As shown in Table 23, Examples 1-3 and Comparative Example except that the ABS resin was changed to an ABS resin with a Charpy impact value of 25 kJ / m ² and the addition amount of brominated bisphenol A was changed to 13 parts by mass. Lead storage batteries were produced in the same manner as in Examples 1 and 2, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed.

As shown in Table 23, in each of Comparative Examples 97 to 101, the produced battery case had a Charpy impact value of 10 kJ / m ² or more and good workability, but the combustibility class was UL94V-0. I was not satisfied.

<Examples 19 to 30 and Comparative Examples 102 to 109>
As shown in Tables 24-27, the ABS resin was changed to an ABS resin having a Charpy impact value of 25 kJ / m ^2, and the addition amount of brominated bisphenol A was 15 parts by mass, 17 parts by mass, 23 parts by mass and 25 parts by mass. Except having changed into the part, lead acid battery was produced like Examples 1-3 and Comparative Examples 1-2, and the same test and measurement as Examples 1-3 and Comparative Examples 1-2 were performed.

As shown in Tables 24 to 27, in Examples 19 to 30 in which the amount of antimony trioxide added is 5 parts by mass or more, the produced battery case has a combustibility class of UL94V-0 and a Charpy impact value. It was 10 kJ / m ² or more, and the workability was also good.

In Comparative Examples 102 to 109 in which the amount of antimony trioxide added is less than 5 parts by mass, the Charpy impact value was 10 kJ / m ² or more and the workability was good. Did not satisfy UL94V-0.

<Comparative Examples 110-114>
As shown in Table 28, Examples 1-3 and Comparative Example except that the ABS resin was changed to an ABS resin having a Charpy impact value of 25 kJ / m ² and the addition amount of brominated bisphenol A was changed to 27 parts by mass. Lead storage batteries were produced in the same manner as in Examples 1 and 2, and the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2 were performed.

As shown in Table 28, in Comparative Examples 110 to 111 in which the addition amount of antimony trioxide is less than 5 parts by mass, the Charpy impact value was 10 kJ / m ² or more, and the workability was good, but the fabrication was performed. The battery case did not satisfy UL94V-0 in the flammability class.

In Comparative Examples 112 to 114 in which the amount of antimony trioxide added is 5 parts by mass or more, the produced battery case had a combustibility class of UL94V-0 and had good workability, but had a Charpy impact value. Was less than 10 kJ / m ² .

  Next, the test was conducted by changing the amount of stearic acid bisamide (SBA) added to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass.

<Examples 31 to 42 and Comparative Examples 115 to 117>
As shown in Tables 29 to 31, Examples 1 to 1 were changed except that the addition amount of stearic acid bisamide was changed to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass. The lead acid battery was produced like 3 and the test and measurement similar to Examples 1-3 were performed.

  As shown in Tables 29 to 31, in Comparative Examples 115 to 117 in which stearic acid bisamide was not added, the flammability class satisfied UL94V-0, and the produced battery case satisfied the flammability class UL94V-0. However, good workability was not obtained.

 In Examples 31 to 42 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

<Examples 43 to 54 and Comparative Examples 118 to 120>
As shown in Tables 32 to 34, Examples 4 to 4 except that the amount of stearic acid bisamide added was changed to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass. A lead storage battery was produced in the same manner as in Example 6, and the same tests and measurements as in Examples 4 to 6 were performed.

 As shown in Tables 32-34, in Comparative Examples 118-120 in which stearic acid bisamide was not added, the flammability class satisfied UL94V-0, and the produced battery case satisfied the flammability class UL94V-0. However, good workability was not obtained.

 In Examples 43 to 54 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

<Examples 55-66 and Comparative Examples 121-123>
As shown in Tables 35 to 37, Examples 13 to 36 except that the amount of stearic acid bisamide added was changed to 0 (not added), 0.1, 0.2, 0.4, and 0.5 parts by mass. The lead acid battery was produced like 15 and the test and measurement similar to Examples 13-15 were performed.

 As shown in Tables 35 to 37, in Comparative Examples 121 to 123 in which stearic acid bisamide was not added, the flammability class satisfied UL94V-0, and the produced battery case satisfied the flammability class UL94V-0. However, good workability was not obtained.

 In Examples 55 to 66 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

<Examples 67 to 78 and Comparative Examples 124 to 126>
As shown in Tables 38-40, Examples 16-16 except that the addition amount of stearic acid bisamide was changed to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass. The lead acid battery was produced like 18 and the test and measurement similar to Examples 16-18 were performed.

 As shown in Tables 38 to 40, in Comparative Examples 124 to 126 in which stearic acid bisamide was not added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0. However, good workability was not obtained.

 In Examples 67 to 78 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

<Examples 79 to 90 and Comparative Examples 127 to 129>
As shown in Tables 41 to 43, Examples 19 to 19 except that the addition amount of stearic acid bisamide was changed to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass. The lead acid battery was produced like 21 and the test and measurement similar to Examples 19-21 were performed.

 As shown in Tables 41 to 43, in Comparative Examples 127 to 129 in which stearic acid bisamide was not added, the flammability class satisfied UL94V-0, and the produced battery case satisfied the flammability class UL94V-0. However, good workability was not obtained.

 In Examples 79 to 90 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

<Examples 91 to 102 and Comparative Examples 130 to 132>
As shown in Tables 44 to 46, Examples 28 to 28 except that the amount of stearic acid bisamide added was changed to 0 (no addition), 0.1, 0.2, 0.4, and 0.5 parts by mass. A lead storage battery was produced in the same manner as in Example 30, and the same tests and measurements as in Examples 28 to 30 were performed.

 As shown in Tables 44 to 46, in Comparative Examples 130 to 132 in which stearic acid bisamide was not added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0. However, good workability was not obtained.

 In Examples 91 to 102 to which stearic acid bisamide was added, the combustibility class satisfied UL94V-0, and the produced battery case satisfied the combustibility class UL94V-0, and good workability was obtained.

According to the present invention, the battery case for the lead storage battery is composed of the resin material having the Charpy impact value of 20 kJ / m ² or more as a main component and the addition of the flame retardant, so the flammability class is UL94V. Even if high combustion resistance satisfying −0 is realized, a battery case for a lead storage battery having a Charpy impact value of 10 kJ / m ² or more can be obtained.

Claims (4)

A battery case for a lead-acid battery formed of a resin material having an additive containing a flame retardant as a main component, an ABS resin having a Charpy impact value of 20 kJ / m ² or more,
The resin material is bromine with respect to 100 parts by mass of the ABS resin so that the flammability class of the battery case satisfies UL94V-0 and the Charpy impact value of the battery case is 10 kJ / m ² or more. A battery case for a lead-acid battery, to which an additive containing 15 to 25 parts by mass of bisphenol A, 5 parts by mass or more of antimony trioxide and 0.1 parts by mass or more of stearic acid bisamide (SBA) is added . ^{2. The} battery case for a lead storage battery according to claim 1, wherein the ABS resin as a main component of the resin material is an ABS resin having a Charpy impact value of 25 kJ / m ² or more.   The lead acid battery which uses the battery case for lead acid batteries of Claim 1 or 2. Per 100 parts by weight of ABS resin Charpy impact value is 20 kJ / m ² or more, 15 to 25 parts by weight of brominated bisphenol A, antimony trioxide 5 parts by mass or more and fatty acid amide and 0.1 part by mass or more Containing additives are added,
The resin material for a battery case for a lead storage battery, wherein the fatty acid amide is stearic acid bisamide (SBA).