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

Lead-acid battery battery, lead-acid battery using lead-acid battery battery, and resin composition of lead-acid battery battery Download PDF

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JP6303651B2
JP6303651B2 JP2014051569A JP2014051569A JP6303651B2 JP 6303651 B2 JP6303651 B2 JP 6303651B2 JP 2014051569 A JP2014051569 A JP 2014051569A JP 2014051569 A JP2014051569 A JP 2014051569A JP 6303651 B2 JP6303651 B2 JP 6303651B2
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battery
lead
battery case
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mass
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JP2015176710A (en
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一郎 向谷
一郎 向谷
覚野　博司
博司 覚野
真也 水杉
真也 水杉
賢二 苅谷
賢二 苅谷
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/143—Fireproof; Explosion-proof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Description

本発明は、鉛蓄電池用の電槽、鉛蓄電池用の電槽を使用した鉛蓄電池及び鉛蓄電池用の電槽の樹脂組成物に関し、より詳細には、制御弁式鉛蓄電池用の電槽、制御弁式鉛蓄電池用の電槽を使用した鉛蓄電池及び制御弁式鉛蓄電池用の電槽の樹脂組成物に関するものである。   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.

制御弁式鉛蓄電池は、メンテナンスフリー、酸霧、ガスの放出がほとんどない等の特長を生かして、ポータブル機器，コードレス機器，コンピュータのバックアップ電源等の無停電電源装置をはじめ、大型の据置用電池や電動車用の主電源、自動車のエンジン始動用としても使用されている。また、オフィスビル、病院等の非常用電源装置、電力負荷平準化用（ピークカット、ピークシフト）電力貯蔵システム、自然エネルギー発電機の出力安定化装置等の産業用電池としても使用されている。   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.

また、他の二次電池に比べ経済性に優れ、安定した性能を有した電池であることから鉛蓄電池の需要は年々増大しており、その用途により高容量化、長寿命化、使用温度の広範囲化、軽量化等の電池に対する要求特性多様化し、要求される品質レベルも年々高くなっている。   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.

鉛蓄電池は、電槽内に配置された電極群と、電解液としての希硫酸との化学反応により充放電を行う。希硫酸は強酸性であり、電解液の漏洩には危険が伴うため、電槽の破損、ひび割れ、劣化に対して十分注意する必要がある。そのため、鉛蓄電池の電槽には、高い耐酸性・耐硫酸性が要求される。   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.

また電槽に破損、ひび割れ等が生じると、電解液が漏洩して周辺機器が損傷する恐れがある。   If the battery case is broken or cracked, the electrolyte may leak and damage peripheral equipment.

さらに鉛蓄電池の電槽には、防災（火災防止）の観点から耐衝撃性、機械的強度及び難燃性が要求されるとともに、高い成形性が要求される。   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.

特開２００２−４２７４８号公報（特許文献１）には、難燃性ポリプロピレン製の電槽が開示されている。また、特開２００６−３４８０９８号公報（特許文献２）には、機械的強度、成形性、難燃性を有するポリカーボネート系樹脂からなる鉛蓄電池ケーシングが開示されている。また、特表２００８−５１９１５３号公報（特許文献３）には、臭素系有機化合物難燃剤と、アンチモン系難燃補助剤と、ステアルアミド系化合物とを含有することにより、難燃性に優れるのみならず、耐侯性及び熱安定性が著しく向上し、衝撃強度、流動性を増加させて加工性を向上させたアクリロニトリル−ブタジエン−スチレン共重合性樹脂（ＡＢＳ樹脂）組成物が開示されている。   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.

特開２００２−４２７４８号公報JP 2002-42748 A 特開２００６−３４８０９８号公報JP 2006-348098 A 特表２００８−５１９１５３号公報Special table 2008-519153 gazette

携帯電話機の基地局等に設置される鉛蓄電池は、災害発生等により商用電源が喪失したときの非常用電源として使用され、復旧するまでの間継続して電力を供給できる電池容量と、不具合なく稼働する信頼性が要求される。特に交通の便の悪い地域では、鉛蓄電池のメンテナンスを頻繁に行うことが困難であるため、長期の安全性と信頼性が求められ、電源システムあるいは鉛蓄電池に何らかの異常が生じて火災に至ったときにも周辺機器に延焼しないことが重要となる。そのため、鉛蓄電池の電槽にも自己消火性を持つ、燃焼性クラスＵＬ９４−Ｖ０の樹脂材料を使用することが要求される。   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.

また、鉛蓄電池を運搬して所定の場所に設置する間、及び蓄電池のメンテナンスを行うときの取り扱いに起因して、鉛蓄電池の電槽に疵、へこみ等がつくことがある。そして、朝晩、季節により変動する設置周囲温度に伴い鉛蓄電池の電槽が膨張収縮し、この疵、へこみ部分に応力が集中することが原因となって、電槽に破損、ひび割れ等が生じることがある。非常用電源として使用される鉛蓄電池は非常時に備えて、通常、満充電の状態でスタンバイしているが、鉛蓄電池の容量を確認、及び鉛蓄電池に不具合が発生しているか否かを調査するために、一定期間毎に放電して点検を行うこともある。点検後は満充電を行い容量回復してスタンバイ状態に戻るが、この点検時の充放電により鉛蓄電池が発熱するため、電槽が膨張収縮し、電槽の破損、ひび割れが発生することもある。   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. .

この電槽の破損部分から漏洩した電解液を介してリーク電流、スパークが発生し鉛蓄電池及び周辺機器が損傷することが考えられる。更に電槽の破損部分を通して、鉛蓄電池収納具との間で短絡が発生することにより鉛蓄電池が高温になり、電槽及び周辺機器が発火し周囲に延焼する恐れがある。そのため、鉛蓄電池の運搬、保守点検時の取り扱いに十分な注意が払われなくとも、電槽に疵、へこみ等がつかないように、優れた耐衝撃性を持つ電槽が要求される。   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.

ＡＢＳ樹脂には、高い衝撃性を有するものがある。しかしながら、耐衝撃性の高いＡＢＳ樹脂は、流動性が低くなるため、加工性が低下する。そのため鉛蓄電池用の電槽をＡＢＳ樹脂により形成する場合には、加工性を維持するために、耐衝撃性の低いＡＢＳ樹脂しか使用することができない問題があった。また、ＡＢＳ樹脂に難燃性を与えるために、難燃剤等を添加すると、ＡＢＳ樹脂の耐衝撃性がさらに低くなってしまう。そのため、従来のＡＢＳ樹脂系の樹脂組成物では、鉛蓄電池の電槽の難燃性及び耐衝撃性を十分に高めることができていない。   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.

本発明の目的は、加工性及び難燃性を十分に高めても耐衝撃性に優れるＡＢＳ樹脂系の鉛蓄電池用の電槽、鉛蓄電池用の電槽を使用した鉛蓄電池及び鉛蓄電池用の電槽の樹脂組成物を提供することにある。   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.

上記課題を解決するために、発明者らは鋭意研究・検討の結果、シャルピー衝撃値が２０ｋＪ／ｍ２以上になるＡＢＳ樹脂が主成分である樹脂材料であれば、燃焼性クラスがＵＬ９４Ｖ−０規格を満足するように難燃剤を添加しても、シャルピー衝撃値が１０ｋＪ／ｍ２以上の鉛蓄電池用の電槽を得られることを見いだした。この知見に基づき、発明者らは、難燃剤として臭素化ビスフェノールＡを、難燃助剤として三酸化アンチモンを用いる場合に、樹脂材料の加工性を高めるために脂肪族アミドを併用する研究を行った。また、シャルピー衝撃値が２０ｋＪ／ｍ２以上になるＡＢＳ樹脂を主成分とした場合の、難燃剤として臭素化ビスフェノールＡと、難燃助剤として三酸化アンチモンとの添加について研究を行った。その結果、鉛蓄電池用の電槽は、成形加工時の加工性が良好で、燃焼性クラスがＵＬ９４Ｖ−０規格を満足し、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、しかも耐硫酸性及び耐酸化性が高い鉛蓄電池用の電槽が得られることを見いだした。本発明は上記知見に基づくものである。 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.

本発明は、ＡＢＳ樹脂が主成分であり、難燃剤を含む添加剤が加えられた樹脂材料によって形成された鉛蓄電池用の電槽を改良の対象とする。本発明では、シャルピー衝撃値が２０ｋＪ／ｍ２以上になるＡＢＳ樹脂を主成分とすることにより、燃焼性クラスがＵＬ９４Ｖ−０を満足する高い耐難燃性が得られるように難燃剤を含む添加剤を加えても、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、しかも高い加工性を有する鉛蓄電池用の電槽を得ることができる。 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.

ここで、ＵＬ９４規格は、安全規格として国際的な影響力を有する米国のＵＬ社（Underwriters Laboratories Inc.）の機器の部品用プラスチック材料の燃焼性試験の規格番号である。   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.

またシャルピー衝撃値とは、ＪＩＳ Ｋ７１１１−１に従い、２５℃雰囲気中にて測定した値であり、具体的には、試料の破壊に要したエネルギーを、試料の破壊前の断面積で割って求めた値であり、この値が高いほど靭性が良く、破壊され難い。   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.

具体的な樹脂材料としては、例えば、添加剤として、臭素化ビスフェノールＡ、三酸化アンチモン及び脂肪酸アミドを添加したものとすることができる。臭素化ビスフェノールＡ、三酸化アンチモン及び脂肪酸アミドの組み合わせは、耐衝撃性と、加工性及び難燃性との両方を十分に高めることができる添加剤の組み合わせである。   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.

本明細書において脂肪酸アミドとは、ステアリン酸アミド、ステアリン酸ビスアミド、ヒドロキシステアリン酸ビスアミド、ｍ−キシリレンビスステアリン酸アミド、Ｎ，Ｎ’−ジステアリルイソフタル酸アミド、Ｎ，Ｎ’−ジステアリルセバシン酸アミド、Ｎ，Ｎ’−ジステアリルアジピン酸アミド、ブチレンビスヒドロキシステアリン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、ヘキサメチレンビスべヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、エチレンビスべヘン酸アミド、エチレンビスヒドロキシステアリン酸アミド、エチレンビスステアリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスカプリル酸アミド、メチレンビスヒドロキシステアリン酸アミド、メチレンビスラウリン酸アミド、メチレンビスステアリン酸アミド等を含むものである。   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.

樹脂材料の具体的な組成としては、シャルピー衝撃値が２０ｋＪ／ｍ２以上になるＡＢＳ樹脂１００質量部に対して、臭素化ビスフェノールＡを１５〜２５質量部、三酸化アンチモンを５質量部以上及び脂肪族アミドを０．１質量部以上に調整した添加剤を加えたものとすることができる。 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.

なお脂肪酸アミドは、例えばステアリン酸ビスアミド（ＳＢＡ）とすることができる。   The fatty acid amide can be, for example, stearic acid bisamide (SBA).

樹脂材料の主成分であるＡＢＳ樹脂は、シャルピー衝撃値が２５ｋＪ／ｍ２以上になるＡＢＳ樹脂であることが好ましい。このようにすると、難燃剤の添加量を増やしても、鉛蓄電池用の電槽のシャルピー衝撃値を確実に１０ｋＪ／ｍ２以上とすることができる。 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.

本発明は、本発明の鉛蓄電池用の電槽を備えた鉛蓄電池または本発明の鉛蓄電池用の電槽用の樹脂材料として把握することもできる。   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.

以下、本発明の鉛蓄電池の実施の形態の構成を詳細に説明する。   Hereinafter, the configuration of the embodiment of the lead storage battery of the present invention will be described in detail.

本発明の実施の形態の鉛蓄電池は、電槽本体及び蓋体を備える電槽と、この電槽の内部に収容される正極板、負極板、セパレータ及び電解液とを有している。   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.

＜電槽＞
電槽は、一方の端部が開口する電槽本体と、電槽本体の開口部を覆う蓋体とを備えている。電槽の内部には、セパレータを介して積層される正極板及び負極板を有する電極群と、この電極群を浸漬させる電解液とが収容される。電槽はＡＢＳ系樹脂材料により構成されている。 <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.

電槽本体は、成形性及び搬送時の無効空間を減らせることから、立方体又は直方体形状とすることが好ましい。しかしながら、一方の端部が開口していれば、特にその形状を限定されるものではなく、多角柱等他の形状とすることができる。また蓋体は、電槽本体と同じ材質により構成されており、電槽本体の一方の端部の開口を覆う。   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.

＜正極板・負極板＞
正極板及び負極板は、格子基板に活物質を保持させたものであり、鋳造格子基板又はエキスパンド格子基板にペースト状活物質を保持させたペースト式極板を用いることができる。また、ガラス繊維を編み上げたチューブの中に鉛合金製の芯を通し、活物質を充填して主に正極板として使用する、クラッド式極板を用いてもよい。 <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.

格子基板の材質は、主原料を鉛とするもので、これにスズ、カルシウム、アンチモン等を添加することができ、特に、カルシウム及びスズを用いることが好ましい。カルシウムを添加することにより、自己放電の割合を減少させることができるが、その際の課題である集電体の腐食の起こり易さをスズの添加により抑制することができる。   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.

ペースト式極板は、クラッド式極板より容易に製造することができる。ペースト状活物質の調製は例えば、一酸化鉛を含んだ鉛粉、水、硫酸等（正極、負極の特性に合わせてカットファイバ−、炭素粉末、リグニン、硫酸バリウム、鉛丹等の添加物を加える場合もある）を混練して作製することができるが、特に限定されるものではない。   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.

＜セパレータ＞
セパレータは、正極板と負極板との間に介在し、正極と負極との短絡を防止する。具体的なセパレータは例えば、ポリエチレン、ガラス不織布、ポリプロピレン等の材料からなる多孔質シート、およびこれらの材料からなる繊維の混織物等から構成することができるが、特に限定されるものではない。 <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.

＜電解液＞
電解液は例えば、希硫酸を精製水で希釈し、質量パーセント濃度で約３０質量％前後に調合したものを、電池容量・寿命等を考慮した適正な濃度に調整したものを用いることができる。なお、鉛蓄電池に要求される特性に合わせて、硫酸マグネシウム、シリカゲル等の添加剤を加えてもよい。 <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.

＜鉛蓄電池＞
本発明の鉛蓄電池は、鉛又は鉛合金製の格子基板にペースト状活物質を保持させたペースト式正負極板を、セパレータを介して交互に積層し、同極性の耳部同士にストラップを溶接して極板群を作製した。この極板群を電槽本体内に配置して蓋体を装着し、電槽内に電解液を注入した後、化成して作製することができる。また、クラッドチューブに鉛粉を充填して製造するクラッド式極板を用いた鉛蓄電池にも適用することができる。 <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.

次に本発明の実施例及び比較例について説明する。なお本発明は、下記の実施例に制限されるものではない。   Next, examples and comparative examples of the present invention will be described. In addition, this invention is not restrict | limited to the following Example.

ＡＢＳ樹脂としてテクノポリマ−株式会社のテクノＡＢＳ１５０を、臭素化ビスフェノールＡとして帝人化成株式会社製のＦＧ−８５００を、三酸化アンチモンとして株式会社日本精鉱製の三酸化アンチモンＭを、（メチレン）ステアリン酸ビスアミドとして日本化成株式会社製のビスアマイドＬＡをそれぞれ使用した。   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.

＜実施例１＞
シャルピー衝撃値が２０ｋＪ／ｍ２になるＡＢＳ樹脂１００質量部に対し、臭素化ビスフェノールＡを２０質量部、三酸化アンチモンを５質量部、及びステアリン酸ビスアミドを０．３質量部添加した樹脂材料を、株式会社池貝がＰＣＭ３０の名称で販売する押出機を使用してコンパウンド（混合）してペレットを成形した。このペレットを、東芝機械製の大型射出成形機ＩＳ８５０ＧＴＷを使用して縦：１７０ｍｍ×横：１０６ｍｍ×高さ：３１２ｍｍの外形寸法で、厚さ：５．０ｍｍの電槽本体を作製した。ここで、「シャルピー衝撃値が２０ｋＪ／ｍ２になるＡＢＳ樹脂」とは、成形後室温になった状態でのシャルピー衝撃値が２０ｋＪ／ｍ２になるＡＢＳ樹脂を意味する。 <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.

作製した電槽内に、正極板及び負極板を、セパレータを介して交互に積層し、同極性の耳部同士にストラップを溶接した極板群を配置し、蓋体を装着後電槽内に電解液を注入して化成を行い鉛蓄電池を作製した。作製した鉛蓄電池について、ＵＬ９４燃焼性試験及びシャルピー衝撃値の測定を行った。   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.

なお、シャルピー衝撃試験はＪＩＳ Ｋ７１１１−１に準拠した試験片を切り出して規定のノッチ加工を行い、株式会社東洋精機製作所製のデジタル衝撃試験機ＤＧ−ＵＢ型を用いて２５℃雰囲気温度中にて測定した。   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.

また作製した電槽の加工性を、離型性及び寸法安定性から評価した。離型性は、作製した電槽を負荷なく金型から脱型／離型できるか否かを示し、寸法安定性は、成形後に離型した電槽が室温までの冷却中に変形したか否かを示す。   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.

＜実施例２〜３及び比較例１〜３＞
三酸化アンチモンの添加量を１，３，４，７，１０質量部に変更した以外は、実施例１と同様にして鉛蓄電池を作製し、実施例１と同様の試験及び測定を行った。 <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.

実施例１〜３及び比較例１〜３の試験結果及び測定結果を表１に示す。なお、表中「ＵＬ９４Ｖ０」欄の「ＮＧ」は、燃焼性クラスがＵＬ９４Ｖ−０を満足しないことを、「ＯＫ」は、燃焼性クラスがＵＬ９４Ｖ−０を満足することをそれぞれ示している。   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.

また、「ＳＰ衝撃」の欄の数値はシャルピー衝撃値の測定結果を示す。「総合評価」欄の「ＮＧ」は、燃焼性クラスがＵＬ９４Ｖ−０を満足していない及び／またはシャルピー衝撃値が１０ｋＪ／ｍ２未満であることを、「ＯＫ」は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、かつ、シャルピー衝撃値が１０ｋＪ／ｍ２以上であることを示している。 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.

さらに、「加工性」の欄の「○」は、作製した電槽を負荷なく金型から脱型／離型でき、成形後に離型した電槽が室温までの冷却中に変形しないことを示し、「×」は、作製した電槽を負荷なく金型から脱型／離型できない及び／または成形後に離型した電槽が室温までの冷却中に変形したことを示している。

Figure 0006303651
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.
Figure 0006303651

表１に示すように、三酸化アンチモンの添加量が５質量部以上である実施例１〜３では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性が良好であった。三酸化アンチモンの添加量が５質量部未満である比較例１〜３では、作製した電槽は、シャルピー衝撃値は実施例１〜３よりも高い数値であり、加工性も良好であったが、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例４〜８＞
表２に示すように、臭素化ビスフェノールＡの添加量を１３質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表２に示すように、臭素化ビスフェノールＡの添加量が１５質量部未満である比較例４〜８ではいずれも、作製した電槽は、シャルピー衝撃値は１０ｋＪ／ｍ２以上であり、加工性は良好であったが、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜実施例４〜１５及び比較例９〜１６＞
表３〜６にそれぞれ示すように、臭素化ビスフェノールＡの添加量を１５質量部、１７質量部、２３質量部及び２５質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651

表３〜６に示すように、三酸化アンチモンの添加量が５質量部以上である実施例４〜１５では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性も良好であった。 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.

三酸化アンチモンの添加量が５質量部未満である比較例９〜１６では、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性は良好であったものの、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例１７〜２１＞
表７に示すように、臭素化ビスフェノールＡの添加量を２７質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表７に示すように、三酸化アンチモンの添加量が５質量部未満である比較例１７〜１８では、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性は良好であったものの、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

三酸化アンチモンの添加量が５質量部以上である比較例１９〜２１では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性が良好であったものの、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

次に樹脂材料の主成分であるＡＢＳ樹脂を、シャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂に変更してＵＬ９４燃焼性試験及びシャルピー衝撃値の測定を行った。ここで、「シャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂」とは、成形後室温になった状態でのシャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂を意味する。 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.

＜比較例２２〜２７＞
表８に示すように、ＡＢＳ樹脂を、シャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂に変更した以外は、比較例１〜３及び実施例１〜３と同様にして鉛蓄電池を作製し、比較例１〜３及び実施例１〜３と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表８に示すように、三酸化アンチモンの添加量が５質量部未満である比較例２２〜２４では、作製した電槽は、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性は良好であるものの、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

三酸化アンチモンの添加量が５以上である比較例２５〜２７では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性は良好であるものの、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

＜比較例２８〜３２＞
表９に示すように、ＡＢＳ樹脂をシャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１３質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表９に示すように、比較例２８〜３２ではいずれも、作製した電槽は、シャルピー衝撃値は１０ｋＪ／ｍ２以上になり、加工性は良好であったが、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例３３〜５７＞
表１０〜１４に示すように、ＡＢＳ樹脂をシャルピー衝撃値が１５ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１５質量部、１７質量部、２３質量部、２５質量部及び２７質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651

表１０〜１４示すように、三酸化アンチモンの添加量が５質量部未満である比較例３３〜３４、３８〜３９、４３〜４４では、シャルピー衝撃値は１０ｋＪ／ｍ２以上になり、加工性は良好であったが、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

三酸化アンチモンの添加量が５質量部以上である比較例３５〜３７、４０〜４２、４５〜４７、５０〜５２及び５５〜５７では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性は良好であったが、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

比較例４８〜４９及び５３〜５４では、加工性は良好であったが、シャルピー衝撃値が１０ｋＪ／ｍ２未満であり、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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. .

次に樹脂材料の主成分であるＡＢＳ樹脂を、シャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂に変更してＵＬ９４燃焼性試験及びシャルピー衝撃値の測定を行った。ここで、「シャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂」とは、成形後室温になった状態でのシャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂を意味する。 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.

＜比較例５８〜６３＞
表１５に示すように、ＡＢＳ樹脂を、シャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂に変更した以外は、比較例１〜３及び実施例１〜３と同様にして鉛蓄電池を作製し、比較例１〜３及び実施例１〜３と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表１５に示すように、三酸化アンチモンの添加量が５質量部未満である比較例５８〜６０では、作製した電槽は、加工性は良好であるものの、シャルピー衝撃値が１０ｋＪ／ｍ２未満であり、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

三酸化アンチモンの添加量が５質量部以上である比較例６１〜６３では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性は良好であるものの、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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.

＜比較例６４〜６８＞
表１６に示すように、ＡＢＳ樹脂をシャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１３質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表１６に示すように、比較例６４〜６８ではいずれも、加工性は良好であったが、作製した電槽は、シャルピー衝撃値は１０ｋＪ／ｍ２未満であり、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例６９〜９３＞
表１７〜２１に示すように、ＡＢＳ樹脂をシャルピー衝撃値が１０ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１５質量部、１７質量部、２３質量部、２５質量部及び２７質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651

表１７〜２１に示すように、三酸化アンチモンの添加量が５質量部未満である比較例６９〜７０、７４〜７５、７９〜８０、８４〜８５及び８９〜９０では、加工性は良好であったが、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足せず、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

三酸化アンチモンの添加量が５質量部以上である比較例７１〜７３、７６〜７８、８１〜８３、８６〜８８及び９１〜９３では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性は良好であったが、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

次に樹脂材料の主成分であるＡＢＳ樹脂を、シャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂に変更してＵＬ９４燃焼性試験及びシャルピー衝撃値の測定を行った。ここで、「シャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂」とは、成形後室温になった状態でのシャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂を意味する。 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.

＜実施例１６〜１８及び比較例９４〜９６＞
表２２に示すように、ＡＢＳ樹脂を、シャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂に変更した以外は、実施例１〜３及び比較例１〜３と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜３と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表２２に示すように、三酸化アンチモンの添加量が５質量部以上である実施例１６〜１８では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性が良好であった。三酸化アンチモンの添加量が５質量部未満である比較例９４〜９６では、作製した電槽は、シャルピー衝撃値は実施例１６〜１８よりも高い数値となり、加工性が良好であったが、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例９７〜１０１＞
表２３に示すように、ＡＢＳ樹脂をシャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１３質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表２３に示すように、比較例９７〜１０１ではいずれも、作製した電槽は、シャルピー衝撃値は１０ｋＪ／ｍ２以上になり、加工性が良好であったが、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜実施例１９〜３０及び比較例１０２〜１０９＞
表２４〜２７に示すように、ＡＢＳ樹脂をシャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を１５質量部、１７質量部、２３質量部及び２５質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651
Figure 0006303651

表２４〜２７に示すように、三酸化アンチモンの添加量が５質量部以上である実施例１９〜３０では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性も良好であった。 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.

三酸化アンチモンの添加量が５質量部未満である比較例１０２〜１０９では、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性は良好であったものの、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

＜比較例１１０〜１１４＞
表２８に示すように、ＡＢＳ樹脂をシャルピー衝撃値が２５ｋＪ／ｍ２になるＡＢＳ樹脂に変更し、臭素化ビスフェノールＡの添加量を２７質量部に変更した以外は、実施例１〜３及び比較例１〜２と同様にして鉛蓄電池を作製し、実施例１〜３及び比較例１〜２と同様の試験及び測定を行った。

Figure 0006303651
<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.
Figure 0006303651

表２８に示すように、三酸化アンチモンの添加量が５質量部未満である比較例１１０〜１１１では、シャルピー衝撃値が１０ｋＪ／ｍ２以上であり、加工性は良好であったものの、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足しなかった。 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.

また三酸化アンチモンの添加量が５質量部以上である比較例１１２〜１１４では、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、加工性が良好であったものの、シャルピー衝撃値が１０ｋＪ／ｍ２未満であった。 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 .

次にステアリン酸ビスアミド（ＳＢＡ）の添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更して試験を行った。   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.

＜実施例３１〜４２及び比較例１１５〜１１７＞
表２９〜３１に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例１〜３と同様にして鉛蓄電池を作製し、実施例１〜３と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表２９〜３１に示すように、ステアリン酸ビスアミドを添加しなかった比較例１１５〜１１７では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。   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.

ステアリン酸ビスアミドを添加した実施例３１〜４２では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

＜実施例４３〜５４及び比較例１１８〜１２０＞
表３２〜３４に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例４〜６と同様にして鉛蓄電池を作製し、実施例４〜６と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表３２〜３４に示すように、ステアリン酸ビスアミドを添加しなかった比較例１１８〜１２０では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。  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.

ステアリン酸ビスアミドを添加した実施例４３〜５４では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

＜実施例５５〜６６及び比較例１２１〜１２３＞
表３５〜３７に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例１３〜１５と同様にして鉛蓄電池を作製し、実施例１３〜１５と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表３５〜３７に示すように、ステアリン酸ビスアミドを添加しなかった比較例１２１〜１２３では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。  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.

ステアリン酸ビスアミドを添加した実施例５５〜６６では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

＜実施例６７〜７８及び比較例１２４〜１２６＞
表３８〜４０に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例１６〜１８と同様にして鉛蓄電池を作製し、実施例１６〜１８と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表３８〜４０に示すように、ステアリン酸ビスアミドを添加しなかった比較例１２４〜１２６では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。  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.

ステアリン酸ビスアミドを添加した実施例６７〜７８では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

＜実施例７９〜９０及び比較例１２７〜１２９＞
表４１〜４３に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例１９〜２１と同様にして鉛蓄電池を作製し、実施例１９〜２１と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表４１〜４３に示すように、ステアリン酸ビスアミドを添加しなかった比較例１２７〜１２９では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。  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.

ステアリン酸ビスアミドを添加した実施例７９〜９０では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

＜実施例９１〜１０２及び比較例１３０〜１３２＞
表４４〜４６に示すように、ステアリン酸ビスアミドの添加量を０（添加せず），０．１，０．２，０．４及び０．５質量部に変更した以外は、実施例２８〜３０と同様にして鉛蓄電池を作製し、実施例２８〜３０と同様の試験及び測定を行った。

Figure 0006303651
Figure 0006303651
Figure 0006303651
 <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.
Figure 0006303651
Figure 0006303651
Figure 0006303651

表４４〜４６に示すように、ステアリン酸ビスアミドを添加しなかった比較例１３０〜１３２では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足したものの、良好な加工性が得られなかった。  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.

ステアリン酸ビスアミドを添加した実施例９１〜１０２では、燃焼性クラスがＵＬ９４Ｖ−０を満足し、作製した電槽は、燃焼性クラスがＵＬ９４Ｖ−０を満足し、良好な加工性が得られた。  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.

本発明によれば、シャルピー衝撃値が２０ｋＪ／ｍ２以上になるＡＢＳ樹脂を主成分として、難燃剤を添加した樹脂材料から鉛蓄電池用の電槽を構成しているので、燃焼性クラスがＵＬ９４Ｖ−０を満足する高い耐燃焼性を実現しても、シャルピー衝撃値が１０ｋＪ／ｍ２以上である鉛蓄電池用の電槽を得ることができる。 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)

シャルピー衝撃値が２０ｋＪ／ｍ2以上になるＡＢＳ樹脂を主成分として、難燃剤を含む添加剤が加えられた樹脂材料によって成形された鉛蓄電池用の電槽であって、
前記樹脂材料は、前記電槽の燃焼性クラスがＵＬ９４Ｖ−０を満足し、且つ前記電槽のシャルピー衝撃値が１０ｋＪ／ｍ2以上となるように、前記ＡＢＳ樹脂１００質量部に対して、臭素化ビスフェノールＡを１５〜２５質量部、三酸化アンチモンを５質量部以上及びステアリン酸ビスアミド（ＳＢＡ）を０．１質量部以上含む添加剤が加えられたことを特徴とする鉛蓄電池用の電槽。 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 . 前記樹脂材料の主成分であるＡＢＳ樹脂は、シャルピー衝撃値が２５ｋＪ／ｍ2以上になるＡＢＳ樹脂であることを特徴とする請求項１に記載の鉛蓄電池用の電槽。 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. 請求項１または２に記載の鉛蓄電池用の電槽を使用した鉛蓄電池。   The lead acid battery which uses the battery case for lead acid batteries of Claim 1 or 2. シャルピー衝撃値が２０ｋＪ／ｍ2以上になるＡＢＳ樹脂１００質量部に対して、臭素化ビスフェノールＡを１５〜２５質量部、三酸化アンチモンを５質量部以上及び脂肪酸アミドを０．１質量部以上含む添加剤が加えられ、
前記脂肪酸アミドは、ステアリン酸ビスアミド（ＳＢＡ）であることを特徴とする鉛蓄電池用の電槽用の樹脂材料。
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).
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