TWI666258B - Battery case for lead-acid battery, lead-acid battery using the battery case, and resin composition for the battery case - Google Patents

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

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TWI666258B
TWI666258B TW104107753A TW104107753A TWI666258B TW I666258 B TWI666258 B TW I666258B TW 104107753 A TW104107753 A TW 104107753A TW 104107753 A TW104107753 A TW 104107753A TW I666258 B TWI666258 B TW I666258B
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lead
mass
battery case
parts
battery
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TW201602217A (en
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向谷一郎
覚野博司
水杉真也
苅谷賢二
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日商日立化成股份有限公司
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    • 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
    • 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
    • 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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Abstract

本案提供用於鉛-酸電池之電池殼，其係由ABS樹脂製成且即使在加工性及阻燃性獲得充分加強時亦提供高耐衝擊性；使用該電池殼之鉛-酸電池；及用於該電池殼之樹脂組成物。用於鉛-酸電池之電池殼係由含有下列之樹脂材料所形成：作為主要組分之沙丕衝擊值為20kJ/m2或更高的ABS樹脂，及以經調整量添加且係經選擇以使該電池殼符合UL94V-0之可燃性等級且具有10kJ/m2或更高之沙丕衝擊值的添加劑。 This case provides a battery case for a lead-acid battery, which is made of ABS resin and provides high impact resistance even when processability and flame retardancy are sufficiently enhanced; a lead-acid battery using the battery case; and A resin composition for the battery case. A battery case for a lead-acid battery is formed of a resin material containing: ABS resin having a sand impact value of 20 kJ / m 2 or higher as a main component, and added in an adjusted amount and selected Additives to make the battery case comply with the flammability rating of UL94V-0 and have a sand impact value of 10 kJ / m 2 or higher.

Description

用於鉛-酸電池之電池殼、使用該電池殼之鉛-酸電池及用於該電池殼之樹脂組成物 Battery case for lead-acid battery, lead-acid battery using the battery case, and resin composition for the battery case

本發明係關於用於鉛-酸電池之電池殼、使用該電池殼之鉛-酸電池及用於該電池殼之樹脂組成物，更具體地係關於用於閥控式鉛-酸電池之電池殼、使用該電池殼之鉛-酸電池、及用於該電池殼之樹脂組成物。 The present invention relates to a battery case for a lead-acid battery, a lead-acid battery using the battery case, and a resin composition for the battery case, and more particularly to a battery for a valve-regulated lead-acid battery A case, a lead-acid battery using the battery case, and a resin composition for the battery case.

閥控式鉛-酸電池(valve-regulated lead-acid battery)係用作不斷電電力供應器，諸如用於可攜式裝置、無線裝置及電腦之備用電力供應器(backup power supply)；大型固定式電池；電動載具之主電力供應器；及用於發動汽車引擎之電力供應器，其優點係無需維護及排放少許酸霧或氣體。閥控式鉛-酸電池亦係用作工業電池，諸如辦公大樓、醫院等之緊急電力供應器，用於平衡電力負載(削減尖峰用電、轉移尖峰用電(peak shifting))之儲能系統，及用於天然能源發電器之輸出 安定化裝置。 Valve-regulated lead-acid battery is used as uninterruptible power supply, such as backup power supply for portable devices, wireless devices and computers; large Stationary batteries; main power supplies for electric vehicles; and power supplies for starting car engines. The advantages are no maintenance and little acid mist or gas emissions. Valve-regulated lead-acid batteries are also used as industrial batteries, emergency power supplies such as office buildings, hospitals, etc., and used to balance power loads (reduction of peak power consumption, peak shifting) of energy storage systems And output for natural energy generators Stabilization device.

鉛-酸電池比其他二次電池經濟，且具有安定性能。因此，對於鉛-酸電池之需求逐年增長。鉛-酸電池所需之性質(諸如較高電容量、較長壽命、較廣可用溫度範圍、及較輕重量)已根據用途而變得多元化，且所需之品質水準逐年變高。 Lead-acid batteries are more economical than other secondary batteries and have stable performance. Therefore, the demand for lead-acid batteries is increasing year by year. The properties required for lead-acid batteries (such as higher capacity, longer life, wider usable temperature range, and lighter weight) have been diversified according to use, and the required level of quality has increased year by year.

鉛-酸電池係經由配置在電池殼中之電極群組與用作電解質的稀硫酸之間的化學反應而充電及放電。該稀硫酸展現強酸性，且電解質洩漏有風險。因此，必須足夠注意電池殼的破裂、龜裂、及劣化。因此，鉛-酸電池之電池殼需要高度耐酸及耐硫酸鹽。 Lead-acid batteries are charged and discharged through a chemical reaction between a group of electrodes arranged in a battery case and dilute sulfuric acid used as an electrolyte. This dilute sulfuric acid exhibits strong acidity and there is a risk of electrolyte leakage. Therefore, sufficient attention must be paid to cracking, cracking, and deterioration of the battery case. Therefore, the battery case of lead-acid batteries needs to be highly resistant to acids and sulfates.

若電池殼破裂或龜裂，電解質會洩漏而危及周圍裝置。 If the battery case is cracked or cracked, the electrolyte may leak and endanger surrounding devices.

從防災(防火)觀點來看，用於鉛-酸電池之電池殼需要耐衝擊性(impact resistance)、機械強度、阻燃性、及高成形性(formability)。 From the standpoint of disaster prevention (fire prevention), a battery case used for a lead-acid battery requires impact resistance, mechanical strength, flame retardancy, and high formability.

JP2002-42748A揭示由阻燃性聚丙烯所製成的電池殼。JP2006-348098A揭示由具有機械強度、成形性、及阻燃性之聚碳酸酯樹脂所製成的鉛-酸電池電池殼。JP 2008-519153 A揭示丙烯腈-丁二烯-苯乙烯共聚物樹脂組成物(ABS樹脂組成物)，其含有溴有機化合物阻燃劑、銻阻燃劑助劑及硬脂醯胺化合物，以提供高阻燃性亦提供顯著改良之耐候性(weather resistance)及熱安定性以及提高之耐衝擊強度及流動性以改善加工性。 JP2002-42748A discloses a battery case made of flame-retardant polypropylene. JP2006-348098A discloses a lead-acid battery case made of a polycarbonate resin having mechanical strength, formability, and flame retardancy. JP 2008-519153 A discloses an acrylonitrile-butadiene-styrene copolymer resin composition (ABS resin composition), which contains a bromine organic compound flame retardant, an antimony flame retardant auxiliary, and a stearylamine compound. Providing high flame resistance also provides significantly improved weather resistance and thermal stability as well as improved impact strength and flowability to improve processability.

安裝在行動電話等之基地台中的鉛-酸電池係用作當商業電力供應因為發生災害等而損失時的緊急電力供應器。因此，此等鉛-酸電池需要容許無問題地連續電力供應直到恢復供電及可靠地工作之電池容量。尤其是在不方便的區域，難以經常維護鉛-酸電池。因此，需要長期安全性及可靠度，重要的是，即使因電力供應系統或鉛-酸電池中異常而著火時，該火不應擴及周圍裝置。因此，用於鉛-酸電池之電池殼要求使用符合UL94V-0之可燃性等級(flammability class)且具有自熄(self-extinguishing)性質的樹脂材料。 Lead-acid batteries installed in base stations such as mobile phones are used as emergency power supplies when commercial power supply is lost due to a disaster or the like. Therefore, these lead-acid batteries need a battery capacity that allows continuous power supply without problems until power is restored and operates reliably. Especially in inconvenient areas, it is difficult to maintain lead-acid batteries often. Therefore, long-term safety and reliability are required, and it is important that the fire should not spread to surrounding devices even if it catches fire due to abnormalities in the power supply system or lead-acid battery. Therefore, battery cases for lead-acid batteries require the use of a resin material that complies with the flammability class of UL94V-0 and has self-extinguishing properties.

用於鉛-酸電池之電池殼在輸送鉛-酸電池以安裝在預定位置或維護鉛-酸電池時的一些狀態下會受損或凹陷。用於鉛-酸電池之電池殼於該電池殼隨著日夜(一天的時間)或周圍溫度的季節波動而膨脹及收縮時會因應力集中在受損或凹陷部分而破裂或龜裂。用作緊急電力供應器之鉛-酸電池在緊急情況下通常以完全充電狀態備用。然而，為了檢查鉛-酸電池之電容量及查核鉛-酸電池中是否發生問題，該等鉛-酸電池係以特定期間之間隔放電以供檢驗。在檢驗之後，將該等鉛-酸電池完全充電以恢復電容量以返回備用狀態。因鉛-酸電池充電及放電以供檢驗時該等鉛-酸電池產生熱，故電池殼會膨脹及收縮而 破裂或龜裂。 The battery case for a lead-acid battery may be damaged or dented in some states when the lead-acid battery is transported to be installed in a predetermined position or when the lead-acid battery is maintained. The battery case for lead-acid batteries will rupture or crack when the battery case expands and contracts with day and night (time of day) or seasonal fluctuations in ambient temperature due to stress concentrated on the damaged or recessed portion. Lead-acid batteries used as emergency power supplies are usually backed up in a fully charged state in emergency situations. However, in order to check the capacity of lead-acid batteries and to check whether problems occur in the lead-acid batteries, the lead-acid batteries are discharged at regular intervals for inspection. After the inspection, the lead-acid batteries were fully charged to restore the capacity to return to the standby state. Because lead-acid batteries generate heat when they are charged and discharged for inspection, the battery case expands and contracts. Cracked or cracked.

可想像經由從該電池殼破裂部分洩漏之電解質產生漏電流或火花而使該鉛-酸電池及周圍裝置受損。若鉛-酸電池與容納該鉛-酸電池之構件之間經由該電池殼的破裂部分發生短路，該鉛-酸電池會變熱，且會在該電池殼中與周圍裝置造成起火，擴及周圍區域。因此，需要具有高耐衝擊性之電池殼，以使得即使在鉛-酸電池輸送及維護期間未小心注意該等鉛-酸電池時亦不會使電池殼受損或凹陷。 It is conceivable that damage to the lead-acid battery and surrounding devices is caused by leakage current or spark generated by the electrolyte leaking from the ruptured part of the battery case. If a short circuit occurs between a lead-acid battery and a component containing the lead-acid battery via the ruptured portion of the battery case, the lead-acid battery will become hot and cause a fire in the battery case and surrounding devices, expanding Surrounding area. Therefore, a battery case having high impact resistance is required so that the battery case may not be damaged or dented even when the lead-acid battery is not carefully taken care of during the transportation and maintenance of the lead-acid battery.

一些ABS樹脂具有高耐衝擊性。然而，具有高耐衝擊性之ABS樹脂具有低流動性，因而降低加工性(processability)。因此，若由ABS樹脂形成用於鉛-酸電池之電池殼，不可避免地使用具有低耐衝擊性之ABS樹脂以維持加工性。若添加阻燃劑等以賦予ABS樹脂阻燃性，該ABS樹脂之耐衝擊性係進一步降低。因此，若使用慣用ABS樹脂組成物，則無法充分強化用於鉛-酸電池之電池殼的阻燃性及耐衝擊性。 Some ABS resins have high impact resistance. However, the ABS resin having high impact resistance has low fluidity, thereby reducing processability. Therefore, if a battery case for a lead-acid battery is formed of ABS resin, it is inevitable to use an ABS resin having low impact resistance to maintain processability. When a flame retardant or the like is added to impart flame resistance to the ABS resin, the impact resistance of the ABS resin is further reduced. Therefore, if a conventional ABS resin composition is used, the flame retardancy and impact resistance of a battery case used for a lead-acid battery cannot be sufficiently enhanced.

本發明之一目的係提供由即使充分強化加工性及阻燃性亦能提供高耐衝擊性之ABS樹脂所製成的用於鉛-酸電池之電池殼、使用該電池殼之鉛-酸電池、及用於該電池殼之樹脂組成物。 An object of the present invention is to provide a battery case for a lead-acid battery made of an ABS resin that can provide high impact resistance even if processability and flame retardancy are sufficiently enhanced, and a lead-acid battery using the same And a resin composition for the battery case.

為了解決前述問題，本案發明人進行認真研究而發 現，沙丕衝擊值(Charpy impact value)為10kJ/m2或更高之用於鉛-酸電池的電池殼，可從含有即使添加阻燃劑以符合UL94V-0標準之可燃性等級時沙丕衝擊值亦為20kJ/m2或更高之ABS樹脂作為主要組分的樹脂材料所製得。根據此等發現，本案發明人對於使用脂肪醯胺來強化樹脂材料之加工性並結合使用溴化雙酚A作為阻燃劑及三氧化二銻作為阻燃劑助劑進行研究。結果發現所得的用於鉛-酸電池之電池殼在形成期間提供良好加工性，符合UL94V-0標準之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且高度耐硫酸鹽及耐酸。因而，本發明係基於上述發現而完成。 In order to solve the foregoing problems, the inventors of the present case conducted earnest research and found that a battery case for a lead-acid battery having a Charpy impact value of 10 kJ / m 2 or higher can be obtained from a battery containing a flame retardant even if it is added. It is made of resin material whose main component is ABS resin with a sand impact value of 20kJ / m 2 or higher when it meets the flammability rating of UL94V-0. Based on these findings, the inventors of the present case have studied the use of aliphatic ammonium to enhance the processability of resin materials, and combined the use of brominated bisphenol A as a flame retardant and antimony trioxide as a flame retardant auxiliary. It was found that the resulting battery case for lead-acid batteries provided good processability during formation, met the flammability rating of the UL94V-0 standard, had a sand impact value of 10kJ / m 2 or higher, and was highly resistant to sulfate and Acid resistance. Therefore, the present invention has been completed based on the above findings.

本發明目的在於改良由包含作為主要組分之ABS樹脂及含有阻燃劑之添加劑的樹脂材料所形成的用於鉛-酸電池之電池殼。根據本發明，沙丕衝擊值為10kJ/m2或更高且具有高加工性的用於鉛-酸電池之電池殼，可由包含即使添加含有阻燃劑之添加劑以使得可獲致符合UL94V-0之可燃性等級的高抗燒性時沙丕衝擊值亦為20kJ/m2或更高之ABS樹脂作為主要組分的樹脂材料獲得。 An 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 a flame retardant-containing additive. According to the present invention, a battery case for a lead-acid battery having an impact value of 10 kJ / m 2 or higher and high processability can be obtained by including, even if an additive containing a flame retardant is added so that UL94V-0 compliance can be obtained A flammability grade with high burn resistance and a sand blast impact value of 20 kJ / m 2 or higher is also obtained by using a resin material whose main component is ABS resin.

UL94標準為由美國Underwriters Laboratories Inc.所確立之用於裝置中之部件的塑膠材料之可燃性的測試之標準數值，且係具有國際影響的安全性標準。 The UL94 standard is a standard value established by Underwriters Laboratories Inc. of the United States for testing the flammability of plastic materials used in components of devices, and is a safety standard with international influence.

用語「沙丕衝擊值」係指根據JIS K 7111-1在大氣中於25℃下所測量的值，具體而言，為將使樣本破裂所需之能量除以該樣本破裂前的橫斷面所獲得之值。隨著沙丕衝 擊值愈大，樣本具有愈高韌度(tenacity)或韌性(toughness)，且更難以破裂。 The term "sand impact value" refers to a value measured at 25 ° C in the atmosphere according to JIS K 7111-1, and specifically, the energy required to break a sample is divided by the cross section before the sample breaks The value obtained. With sand rushing The larger the hit value, the higher the tenacity or toughness of the sample, and the more difficult it is to break.

樹脂材料之一具體實例可含有添加於其中作為添加劑之溴化雙酚A、三氧化二銻、及脂肪醯胺(fatty acid amide)。溴化雙酚A、三氧化二銻、及脂肪醯胺之組合為可充分強化耐衝擊性、加工性及阻燃性全部的添加劑之組合。 One specific example of the resin material may contain brominated bisphenol A, antimony trioxide, and fatty acid amide added as additives. The combination of brominated bisphenol A, antimony trioxide, and aliphatic ammonium is a combination of additives that can fully enhance all of impact resistance, processability, and flame retardancy.

本文所使用之「脂肪醯胺」包括硬脂醯胺(stearic acid amide)、雙硬脂醯胺(bis-stearic acid amide)、雙-羥基硬脂醯胺(bis-hydroxystearic acid amide)、間伸二甲苯基-雙-硬脂醯胺(m-xylylene-bis-stearic acid amide)、N,N'-二硬脂基異酞醯胺(N,N'-distearyl isophthalic acid amide)、N,N'-二硬脂基癸二醯胺(N,N'-distearyl sebacic acid amide)、N,N'-二硬脂基己二醯胺(N,N'-distearyl adipic acid amide)、伸丁基-雙-羥基硬脂醯胺(butylene-bis-hydroxystearic acid amide)、六亞甲基-雙-羥基硬脂醯胺(hexamethylene-bis-hydroxystearic acid amide)、六亞甲基-雙-蘿醯胺(hexamethylene-bis-behenic acid amide)、六亞甲基-雙-硬脂醯胺(hexamethylene-bis-stearic acid amide)、伸乙基-雙-蘿醯胺(ethylene-bis-behenic acid amide)、伸乙基-雙-羥基硬脂醯胺(ethylene-bis-hydroxystearic acid amide)、伸乙基-雙-硬脂醯胺(ethylene-bis-stearic acid amide)、伸乙基-雙-月桂醯胺(ethylene-bis-lauric acid amide)、 伸乙基-雙-癸醯胺(ethylene-bis-capric acid amide)、伸乙基-雙-辛醯胺(ethylene-bis-caprylic acid amide)、亞甲基-雙-羥基硬脂醯胺(methylene-bis-hydroxystearic acid amide)、亞甲基-雙-月桂醯胺(methylene-bis-lauric acid amide)、及亞甲基-雙-硬脂醯胺(methylene-bis-stearic acid amide)。 As used herein, `` fatty ammonium '' includes stearic acid amide, bis-stearic acid amide, bis-hydroxystearic acid amide, and stannic acid. M-xylylene-bis-stearic acid amide, N, N'-distearyl isophthalic acid amide, N, N ' -N, N'-distearyl sebacic acid amide, N, N'-distearyl adipic acid amide, butylene- Butylene-bis-hydroxystearic acid amide, hexamethylene-bis-hydroxystearic acid amide, hexamethylene-bis-hydroxystearic acid amide, hexamethylene-bis-hydroxystearic acid amide hexamethylene-bis-behenic acid amide), hexamethylene-bis-stearic acid amide, ethylene-bis-behenic acid amide, Ethyl-bis-hydroxystearic acid amide, ethylene-bis-stearic acid amide, ethylene-bis-stearic acid amide, ethylene-bis-stearic acid amide ethylene-bis-lauric acid amide ), Ethylene-bis-capric acid amide, ethylene-bis-caprylic acid amide, methylene-bis-caprylic acid amide methylene-bis-hydroxystearic acid amide), methylene-bis-lauric acid amide, and methylene-bis-stearic acid amide.

在樹脂材料之一具體組成物中，以每100質量份之沙丕衝擊值為20kJ/m2或更高之ABS樹脂計，添加劑可含有15至25質量份之溴化雙酚A、5質量份或更多之三氧化二銻、及0.1質量份或更多之脂肪醯胺。 In a specific composition of the resin material, the additive may contain 15 to 25 parts by mass of brominated bisphenol A, 5 parts by mass based on a sand resin impact value of 20 kJ / m 2 or higher per 100 parts by mass. Parts or more of antimony trioxide, and 0.1 parts by mass or more of fatty ammonium.

脂肪醯胺可為例如雙-硬脂醯胺。 The fatty amidamine may be, for example, bis-stearylamine.

作為該樹脂材料之主要組分的ABS樹脂的沙丕衝擊值較佳為25kJ/m2或更高。此確保即使所添加之阻燃劑的量增加時用於鉛-酸電池之電池殼的沙丕衝擊值亦為10kJ/m2或更高。 The sand impact value of the ABS resin as a main component of the resin material is preferably 25 kJ / m 2 or higher. This ensures that the sand impact value of the battery case for lead-acid batteries is 10 kJ / m 2 or higher even when the amount of the added flame retardant is increased.

本發明亦可實施為包括根據本發明之電池殼的鉛-酸電池，或用於根據本發明之電池殼的樹脂材料。 The present invention can also be implemented as a lead-acid battery including a battery case according to the present invention, or a resin material for a battery case according to the present invention.

下文將詳細說明根據本發明實施態樣之鉛-酸電池的構造。 Hereinafter, the configuration of a lead-acid battery according to an embodiment of the present invention will be described in detail.

根據本發明實施態樣之鉛-酸電池包括包含殼體及蓋構件之電池殼、以及容納在該電池殼內的正極、負極、分隔件、及電解質。 A lead-acid battery according to an embodiment of the present invention includes a battery case including a case and a cover member, and a positive electrode, a negative electrode, a separator, and an electrolyte contained in the battery case.

<電池殼> <Battery case>

電池殼包括在一端部分具有開口的殼體，及覆蓋該殼體之開口的蓋構件。包括經由分隔件堆疊之正極及負極的電極群組與浸漬該電極群組之電解質係容納在該電池殼內。該電池殼係由ABS樹脂材料所形成。 The battery case includes a case having an opening at one end portion, and a cover member covering the opening of the case. An electrode group including a positive electrode and a negative electrode stacked through a separator and an electrolyte impregnating the electrode group are contained in the battery case. The battery case is formed of an ABS resin material.

為了獲致良好成形性及減少轉移期間的空隙(void space)，殼體較佳為立方體或矩形平行六面體形狀。然而，只要殼體在一端部分具有開口，該殼體之形狀無特定限制，且該殼體可具有不同形狀，諸如多邊柱(polygonal column)形。蓋構件係由與殼體相同材料所構成，且覆蓋該殼體一端部分的開口。 In order to obtain good formability and reduce void space during transfer, the shell is preferably a cubic or rectangular parallelepiped shape. However, as long as the case has an opening at one end portion, the shape of the case is not particularly limited, and the case may have a different shape, such as a polygonal column shape. The cover member is made of the same material as the casing and covers an opening at one end portion of the casing.

<正極及負極> <Positive and negative electrodes>

正極及負極具有固持在柵基材(grid substrate)上之活性材料。可使用將糊狀活性材料固持在鑄造之柵基材(cast grid substrate)或膨脹柵基材(expanded grid substrate)上的糊型電極(Paste-type electrode)作為正極及負極。亦可使用藉由將由鉛合金所製成的芯棒***編織玻璃纖維管(braided glass fiber tube)且以活性材料填充該管所製備的包覆型電極(Clad-type electrode)主要作為正極。 The positive electrode and the negative electrode have an active material held on a grid substrate. As a positive electrode and a negative electrode, a paste-type electrode in which a pasty active material is held on a cast grid substrate or an expanded grid substrate can be used. A clad-type electrode prepared by inserting a core rod made of a lead alloy into a braided glass fiber tube and filling the tube with an active material can also be used as the positive electrode.

柵基材(grid substrate)含有鉛作為主要組分，及可含有錫、鈣、銻等。特別是，柵基材較佳含有鈣及錫。添 加鈣可降低自放電之速率。然而當添加鈣時，電流收集器可能會腐蝕。因此，可添加錫來抑制電流收集器的腐蝕傾向。 A grid substrate contains lead as a main component, and may contain tin, calcium, antimony, and the like. In particular, the gate substrate preferably contains calcium and tin. add Adding calcium can reduce the rate of self-discharge. However, when calcium is added, the current collector may corrode. Therefore, tin can be added to suppress the corrosion tendency of the current collector.

糊型電極可比包覆型電極更容易製造。糊狀活性材料可藉由捏合含有一氧化鉛之鉛粉末、水、硫酸等(根據正極及負極之性質，有時有添加劑，諸如切短纖維(cut fiber)、碳粉末、木質素、硫酸鋇、及鉛丹)來製造。然而，糊狀活性材料之製備無特定限制。 Pasted electrodes can be more easily manufactured than covered electrodes. Pasty active materials can be prepared by kneading lead powder containing lead monoxide, water, sulfuric acid, etc. (depending on the properties of the positive and negative electrodes, there are sometimes additives such as cut fiber, carbon powder, lignin, sulfuric acid Barium, and lead)). However, the preparation of the pasty active material is not particularly limited.

<分隔件> <Divider>

將分隔件插置於正極與負極之間以防止該正極與負極之間短路。分隔件之具體實例包括由諸如聚乙烯、玻璃不織布(glass non-woven fabric)、及聚丙烯等材料以及由此等材料所製成之纖維的摻合織物所製成的多孔片材。然而，分隔件無特定限制。 A separator is interposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode. Specific examples of the separator include porous sheets made of materials such as polyethylene, glass non-woven fabric, and polypropylene, and blended fabrics of fibers made from these materials. However, the separator is not particularly limited.

<電解質> <Electrolyte>

電解質可例如藉由以純水稀釋稀硫酸至質量百分比濃度為約30%，然後考慮電池之電容量、壽命等而調整濃度至適當值來製備。可根據鉛-酸電池所需之性質而添加諸如硫酸鎂及矽膠之添加劑。 The electrolyte can be prepared, for example, by diluting dilute sulfuric acid with pure water to a concentration of about 30% by mass, and then adjusting the concentration to an appropriate value in consideration of the battery capacity, life, and the like. Additives such as magnesium sulfate and silicone can be added depending on the properties required for lead-acid batteries.

<鉛-酸電池> <Lead-acid battery>

糊狀活性材料係固持在由鉛或鉛合金所製成之柵基材 上的糊型正極及負極係經由分隔件交替堆疊。條帶(strap)係熔接至相同極性的凸緣(lug)部分。如此，製造電極群組。然後將該電極群組配置於殼體中，且將蓋構件接置於該殼體上。之後，將電解質倒入該電池殼而獲得未成形鉛-酸電池，然後完成該鉛-酸電池。本發明亦可應用於使用藉由以鉛粉末填充包覆管(clad tube)所製造之包覆型電極的鉛-酸電池。 Paste-like active material is held on a grid substrate made of lead or lead alloy The pasted positive electrodes and negative electrodes are alternately stacked via a separator. The strips are welded to the lug portions of the same polarity. In this way, an electrode group is manufactured. The electrode group is then arranged in a casing, and a cover member is attached to the casing. After that, the electrolyte was poured into the battery case to obtain an unshaped lead-acid battery, and then the lead-acid battery was completed. The present invention is also applicable to a lead-acid battery using a covered electrode manufactured by filling a clad tube with lead powder.

[實施例] [Example]

接著，將說明本發明之實施例及比較例。本發明不局限於下述實施例。 Next, examples and comparative examples of the present invention will be described. The invention is not limited to the examples described below.

使用由Techno Polymer Co.,Ltd.所製造之Techno ABS 150作為ABS樹脂。使用由Teijin Ltd.所製造之FG-8500作為溴化雙酚A。使用由Nihon Seiko Co.,Ltd.所製造之Antimony Trioxide M作為三氧化二銻。使用由Nippon Kasei Chemical Co.,Ltd.所製造之Bisamide LA作為(亞甲基-)雙-硬脂醯胺。 As the ABS resin, Techno ABS 150 manufactured by Techno Polymer Co., Ltd. was used. As brominated bisphenol A, FG-8500 manufactured by Teijin Ltd. was used. As the antimony trioxide, Antimony Trioxide M manufactured by Nihon Seiko Co., Ltd. was used. As (methylene-) bis-stearylamine, Bisamide LA manufactured by Nippon Kasei Chemical Co., Ltd. was used.

<實施例1> <Example 1>

將以每100質量份之沙丕衝擊值為20kJ/m2的ABS樹脂計為20質量份之溴化雙酚A(下文亦稱為「溴化BPA」)、5質量份之三氧化二銻(Sb2O3)及0.3質量份之雙-硬脂醯胺(下文亦稱為「BSA」)添加至樹脂材料。該樹脂材料係使用由Ikegai Corp.以PCM 30銷售之 擠製機來混練(混合)以形成九粒。使用由Toshiba Machine Co.,Ltd.所製造之大型射出成形機IS850GTW加工該等丸粒以製造外部尺寸為170mm(垂直)、106mm(水平)、及312mm(高度)且厚度為5.0mm之殼體。「沙丕衝擊值為20kJ/m2之ABS樹脂」一辭意指在成形後於室溫下之沙丕衝擊值為20kJ/m2之ABS樹脂。 20 mass parts of brominated bisphenol A (hereinafter also referred to as "brominated BPA") and 5 mass parts of antimony trioxide based on 100 mass parts of ABS resin with a sand impact value of 20 kJ / m 2 (Sb 2 O 3 ) and 0.3 parts by mass of bis-stearylamine (hereinafter also referred to as “BSA”) were added to the resin material. This resin material was kneaded (mixed) using an extruder sold under the PCM 30 by Ikegai Corp. to form nine pellets. These pellets were processed using a large injection molding machine IS850GTW manufactured by Toshiba Machine Co., Ltd. to manufacture a case having outer dimensions of 170 mm (vertical), 106 mm (horizontal), and 312 mm (height) and a thickness of 5.0 mm . The term “ABS resin having a sand impact value of 20 kJ / m 2 ” means an ABS resin having a sand impact value of 20 kJ / m 2 at room temperature after forming.

電極群組係藉由經由分隔件交替堆疊正極及負極且將條帶(strap)熔接至相同極性之凸緣(lug)部分來製備，且係配置在所製造之電池殼中。鉛-酸電池係藉由將蓋構件安裝在殼體上，將電解質倒入該電池殼，且成形鉛-酸電池所製備。根據UL94標準對所製造之鉛-酸電池進行可燃性測試及測量沙丕衝擊值。 The electrode group is prepared by alternately stacking a positive electrode and a negative electrode through a separator, and welding a strap to a lug portion of the same polarity, and is arranged in a manufactured battery case. Lead-acid batteries are prepared by mounting a cover member on a case, pouring an electrolyte into the battery case, and forming a lead-acid battery. The flammability test of lead-acid batteries manufactured according to UL94 standard and the measurement of sand impact value.

符合JIS K 7111-1之測試塊係藉由裁切且形成規定的凹口所製備，以及在大氣中於25℃下使用由Toyo Seiki Seisaku-sho,Ltd.所製造之數位衝擊測試機DG-UB來測量沙丕衝擊值。 A test block conforming to JIS K 7111-1 is prepared by cutting and forming a prescribed notch, and using a digital impact tester DG- manufactured by Toyo Seiki Seisaku-sho, Ltd. at 25 ° C in the atmosphere. UB to measure sand blast impact value.

所製造之電池殼的加工性係基於脫模性(mold releasability)及尺寸穩定性(dimensional stability)之觀點而評估。脫模性表示所製造之電池殼能否無負載地從模具移出/脫離。尺寸穩定性表示在成形之後從模具脫離之電池殼於冷卻至室溫時是否變形。 The workability of the manufactured battery case was evaluated based on the viewpoints of mold releasability and dimensional stability. Releasability indicates whether the manufactured battery case can be removed / detached from the mold without load. The dimensional stability indicates whether the battery case disengaged from the mold after forming is deformed when cooled to room temperature.

<實施例2及3以及比較例1至3> <Examples 2 and 3 and Comparative Examples 1 to 3>

鉛-酸電池係以與實施例1相同方式製造，惟獨三氧 化二銻之添加量改成1、3、4、7、及10質量份，且對所得之鉛-酸電池進行與實施例1相同的測試及測量。 The lead-acid battery was manufactured in the same manner as in Example 1, except that The added amount of antimony bismuth was changed to 1, 3, 4, 7, and 10 parts by mass, and the obtained lead-acid battery was subjected to the same test and measurement as in Example 1.

實施例1至3以及比較例1至3之測試結果及測量結果係表示於表1。在該表之「UL94V-0」欄中，「NG」表示未符合UL94V-0之可燃性等級，而「OK」表示符合UL94V-0之可燃性等級。 The test results and measurement results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. In the "UL94V-0" column of the table, "NG" indicates that it does not meet the flammability rating of UL94V-0, and "OK" indicates that it meets the flammability rating of UL94V-0.

「SP衝擊」欄中之值表示沙丕衝擊值的測量結果。在「綜合評估」欄中，「NG」表示不符合UL94V-0之可燃性等級及/或沙丕衝擊值低於10kJ/m2，而「OK」表示符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高。 The value in the "SP impact" column indicates the measurement result of the sand impact value. In the "comprehensive assessment" column, "NG" means that do not meet flammability rating of UL94V-0 and / or sand pi impact value of less than 10kJ / m 2, and "OK" indicates compliance with flammability rating of UL94V-0 and sand丕 The impact value is 10kJ / m 2 or higher.

在「加工性」欄中，「o」表示所製造之電池殼可無負載地從模具移出/脫離且從該模具脫離之電池殼在成形之後於冷卻至室溫時未變形，而「x」表示所製造之電池殼無法在無負載下從模具移出/脫離及/或從模具脫離之電池殼在成形之後於冷卻至室溫時變形。 In the "workability" column, "o" means that the manufactured battery case can be removed / detached from the mold without load and the battery case released from the mold is not deformed when cooled to room temperature after forming, and "x" Indicates that the manufactured battery case cannot be removed / detached from the mold under no load and / or the battery case deformed when cooled to room temperature after forming.

在三氧化二銻之添加量為5質量份或更多之實施例1至3中，如表1所示，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。在三氧化二銻之添加量少於5質量份之比較例1至3中，所製造之電池殼的沙丕衝擊值高於實施例1至3且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Examples 1 to 3 in which the added amount of antimony trioxide is 5 parts by mass or more, as shown in Table 1, the manufactured battery case complies with the flammability rating of UL94V-0, and the sand impact value is 10kJ / m 2 or higher, and provides good processability. In Comparative Examples 1 to 3 in which the added amount of antimony trioxide is less than 5 parts by mass, the sand impact value of the manufactured battery case is higher than that of Examples 1 to 3 and provides good processability, but does not meet UL94V-0 Flammability rating.

<比較例4至8> <Comparative Examples 4 to 8>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨溴化雙酚A之添加量如表2所示改成13質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 13 parts by mass as shown in Table 2, and the resulting lead-acid batteries were changed. The same tests and measurements were performed as in Examples 1 to 3 and Comparative Examples 1 and 2.

在溴化雙酚A之添加量係如表2所示少於15質量份的所有比較例4至8中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In all Comparative Examples 4 to 8 in which the added amount of brominated bisphenol A was less than 15 parts by mass as shown in Table 2, the manufactured battery case had a sand impact value of 10 kJ / m 2 or more and provided good results. Processability, but does not meet the flammability rating of UL94V-0.

<實施例4至15以及比較例9至16> <Examples 4 to 15 and Comparative Examples 9 to 16>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨溴化雙酚A之添加量如表3至6所示分別改成15質量份、17質量份、23質量份、及25質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 15 parts by mass, 17 parts by mass, and 23 as shown in Tables 3 to 6, respectively. Parts by mass and 25 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2.

在三氧化二銻之添加量為5質量份或更多之實施例4至15中，如表3至6所示，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 4 to 15 in which the amount of antimony trioxide is 5 parts by mass or more, as shown in Tables 3 to 6, the manufactured battery cases meet the flammability rating of UL94V-0, and the sand impact value is 10kJ / m 2 or higher, and provides good processability.

在三氧化二銻之添加量少於5質量份之比較例9至16中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 9 to 16 in which the added amount of antimony trioxide is less than 5 parts by mass, the sanding impact value of the manufactured battery case is 10 kJ / m 2 or higher and provides good processability, but does not meet UL94V- 0 flammability rating.

<比較例17至21> <Comparative Examples 17 to 21>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨溴化雙酚A之添加量如表7所示改成27質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the addition amount of brominated bisphenol A was changed to 27 parts by mass as shown in Table 7, and the obtained lead-acid batteries were changed. The same tests and measurements were performed as in Examples 1 to 3 and Comparative Examples 1 and 2.

在三氧化二銻之添加量如表7所示少於5質量份的比較例17及18中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 17 and 18 in which the added amount of antimony trioxide is less than 5 parts by mass as shown in Table 7, the sand impact value of the manufactured battery case was 10 kJ / m 2 or more and provided good processability, However, it does not meet the flammability rating of UL94V-0.

在三氧化二銻之添加量為5質量份或更多之比較例19至21中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 19 to 21 in which the added amount of antimony trioxide is 5 parts by mass or more, the manufactured battery case complies with the flammability rating of UL94V-0 and provides good processability, but the sand impact value is less than 10kJ / m 2 .

其次，作為樹脂材料之主要組分的ABS樹脂係改成沙丕衝擊值為15kJ/m2之ABS樹脂，且根據UL94標準對所製造的鉛-酸電池進行可燃性測試及測量沙丕衝擊值。「沙丕衝擊值為15kJ/m2之ABS樹脂」一辭意指在成形後於室溫下之沙丕衝擊值為15kJ/m2之ABS樹脂。 Secondly, the ABS resin, which is the main component of the resin material, was changed to an ABS resin with a sand impact value of 15 kJ / m 2 , and the flammability test of the lead-acid battery manufactured according to UL94 standard and the sand impact value were measured . The term "ABS resin having a sand impact value of 15 kJ / m 2 " means an ABS resin having a sand impact value of 15 kJ / m 2 at room temperature after molding.

<比較例22至27> <Comparative Examples 22 to 27>

鉛-酸電池係以與比較例1至3以及實施例1至3相同方式製造，惟獨將ABS樹脂改成如表8所示沙丕衝擊值為15kJ/m2之ABS樹脂，對所得之鉛-酸電池進行與比較例1至3以及實施例1至3相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Comparative Examples 1 to 3 and Examples 1 to 3, except that the ABS resin was changed to an ABS resin having a sand impact value of 15 kJ / m 2 as shown in Table 8. -Acid batteries perform the same tests and measurements as Comparative Examples 1 to 3 and Examples 1 to 3.

在三氧化二銻之添加量如表8所示少於5質量份的比較例22至24中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 22 to 24 in which the added amount of antimony trioxide is less than 5 parts by mass as shown in Table 8, the manufactured battery case has a sand impact value of 10 kJ / m 2 or more and provides good processability. However, it does not meet the flammability rating of UL94V-0.

在三氧化二銻之添加量為5質量份或更多之比較例25至27中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 25 to 27 in which the added amount of antimony trioxide is 5 parts by mass or more, the manufactured battery case complies with the flammability rating of UL94V-0 and provides good processability, but the sand impact value is less than 10kJ / m 2 .

<比較例28至32> <Comparative Examples 28 to 32>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨將ABS樹脂改成如表9所示沙丕衝擊值為15kJ/m2之ABS樹脂，對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the ABS resin was changed to an ABS resin with a sand impact value of 15 kJ / m 2 as shown in Table 9. -Acid batteries perform the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2.

在所有比較例28至32中，如表9所示，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In all Comparative Examples 28 to 32, as shown in Table 9, the sand impact value of the manufactured battery case was 10 kJ / m 2 or higher and provided good processability, but did not meet the flammability rating of UL94V-0.

<比較例33至57> <Comparative Examples 33 to 57>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨如表10至14所示，將ABS樹脂改成沙丕衝擊值為15kJ/m2之ABS樹脂且溴化雙酚A之添加分別改為15質量份、17質量份、23質量份、25質量份、及27質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that as shown in Tables 10 to 14, the ABS resin was changed to an ABS resin with a sand impact value of 15 kJ / m 2 and bromine. The addition of bisphenol A was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass, and 27 parts by mass, respectively, and the obtained lead-acid batteries were subjected to Examples 1 to 3 and Comparative Examples 1 and 2 Same test and measurement.

在三氧化二銻之添加量如表10至14所示少於5質量份的比較例33、34、38、39、43、及44中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 33, 34, 38, 39, 43, and 44 in which the amount of antimony trioxide added was less than 5 parts by mass as shown in Tables 10 to 14, the sand impact value of the manufactured battery case was 10 kJ / m 2 or higher and provides good processability, but does not meet the flammability rating of UL94V-0.

在三氧化二銻之添加量為5質量份或更多之比較例35至37、40至42、45至47、50至52、及55至57中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 35 to 37, 40 to 42, 45 to 47, 50 to 52, and 55 to 57 in which the added amount of antimony trioxide was 5 parts by mass or more, the manufactured battery cases conformed to UL94V-0. Flammability grade and provides good processability, but sand impact value is less than 10kJ / m 2 .

在三氧化二銻之添加量少於5質量份之比較例48、49、53及54中，所製造之電池殼提供良好加工性，但沙丕衝擊值低於10kJ/m2，且不符合UL94V-0之可燃性等級。 In Comparative Examples 48, 49, 53, and 54 in which the amount of antimony trioxide was less than 5 parts by mass, the manufactured battery case provided good processability, but the sand impact value was less than 10 kJ / m 2 and did not meet Flammability rating of UL94V-0.

接著，作為樹脂材料之主要組分的ABS樹脂係改成沙丕衝擊值為10kJ/m2之ABS樹脂，且根據UL94標準對所製造的鉛-酸電池進行可燃性測試及測量沙丕衝擊值。「沙丕衝擊值為10kJ/m2之ABS樹脂」一辭意指在成形後於室溫下之沙丕衝擊值為10kJ/m2之ABS樹脂。 Next, the ABS resin as the main component of the resin material was changed to an ABS resin with a sand impact value of 10 kJ / m 2 , and the flammability test of the lead-acid battery manufactured according to the UL94 standard and the sand impact value were measured. . The term "ABS resin having a sand impact value of 10 kJ / m 2 " means an ABS resin having a sand impact value of 10 kJ / m 2 at room temperature after molding.

<比較例58至63> <Comparative Examples 58 to 63>

鉛-酸電池係以與實施例1至3以及比較例1至3相同方式製造，惟獨將ABS樹脂改成如表15所示沙丕衝擊值為10kJ/m2之ABS樹脂，對所得之鉛-酸電池進行與比較例1至3以及實施例1至3相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3, except that the ABS resin was changed to an ABS resin with a sand impact value of 10 kJ / m 2 as shown in Table 15. -Acid batteries perform the same tests and measurements as Comparative Examples 1 to 3 and Examples 1 to 3.

在三氧化二銻之添加量如表15所示少於5質量份之比較例58至60中，所製造之電池殼提供良好加工性，但沙丕衝擊值低於10kJ/m2，且不符合UL94V-0之可燃性等級。 In Comparative Examples 58 to 60 in which the added amount of antimony trioxide is less than 5 parts by mass as shown in Table 15, the manufactured battery case provided good processability, but the sand impact value was less than 10 kJ / m 2 and Meets UL94V-0 flammability rating.

在三氧化二銻之添加量為5質量份或更多之比較例61至63中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 61 to 63 in which the added amount of antimony trioxide is 5 parts by mass or more, the manufactured battery case complies with the flammability rating of UL94V-0 and provides good processability, but the sand impact value is less than 10kJ / m 2 .

<比較例64至68> <Comparative Examples 64 to 68>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨將ABS樹脂改成如表16所示沙丕衝擊值為10kJ/m2之ABS樹脂，對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the ABS resin was changed to an ABS resin with a sand impact value of 10 kJ / m 2 as shown in Table 16. -Acid batteries perform the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 and 2.

在所有比較例64至68中，如表16所示，所製造之電池殼提供良好加工性，但沙丕衝擊值低於10kJ/m2，且不符合UL94V-0之可燃性等級。 In all Comparative Examples 64 to 68, as shown in Table 16, the manufactured battery cases provided good processability, but the sand impact value was less than 10 kJ / m 2 and did not meet the flammability rating of UL94V-0.

<比較例69至93> <Comparative Examples 69 to 93>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨如表17至21所示，將ABS樹脂改成沙丕衝擊值為10kJ/m2之ABS樹脂且溴化雙酚A之添加量分別改為15質量份、17質量份、23質量份、25質量份、及27質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that as shown in Tables 17 to 21, the ABS resin was changed to an ABS resin with a sand impact value of 10 kJ / m 2 and bromine. The addition amount of bisphenol A was changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, 25 parts by mass, and 27 parts by mass, respectively, and the obtained lead-acid batteries were subjected to the same procedures as in Examples 1 to 3 and Comparative Example 1. And 2 the same test and measurement.

在三氧化二銻之添加量如表17至21所示少於5質量份的比較例69、70、74、75、79、80、84、85、89、及90中，所製造之電池殼提供良好加工性，但不符合UL94V-0之可燃性等級且沙丕衝擊值低於10kJ/m2。 Battery cases manufactured in Comparative Examples 69, 70, 74, 75, 79, 80, 84, 85, 89, and 90 in which the added amount of antimony trioxide is less than 5 parts by mass as shown in Tables 17 to 21 Provides good processability, but does not meet the flammability rating of UL94V-0 and the sand impact value is less than 10kJ / m 2 .

在三氧化二銻之添加量為5質量份或更多之比較例71至73、76至78、81至83、86至88、及91至93中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 71 to 73, 76 to 78, 81 to 83, 86 to 88, and 91 to 93 in which the antimony trioxide was added in an amount of 5 parts by mass or more, the manufactured battery cases conformed to UL94V-0. Flammability grade and provides good processability, but sand impact value is less than 10kJ / m 2 .

接著，作為樹脂材料之主要組分的ABS樹脂係改成沙丕衝擊值為25kJ/m2之ABS樹脂，且根據UL94標準對所製造的鉛-酸電池進行可燃性測試及測量沙丕衝擊值。「沙丕衝擊值為25kJ/m2之ABS樹脂」一辭意指在成形後於室溫下之沙丕衝擊值為25kJ/m2之ABS樹脂。 Next, the ABS resin, which is the main component of the resin material, was changed to an ABS resin with a sand impact value of 25 kJ / m 2 , and the flammability test of the lead-acid battery manufactured according to UL94 standard and the sand impact impact value were measured. . The term "ABS resin having a sand impact value of 25 kJ / m 2 " means an ABS resin having a sand impact value of 25 kJ / m 2 at room temperature after molding.

<實施例16至18以及比較例94至96> <Examples 16 to 18 and Comparative Examples 94 to 96>

鉛-酸電池係以與實施例1至3以及比較例1至3相同方式製造，惟獨將ABS樹脂改成如表22所示沙丕衝擊值為25kJ/m2之ABS樹脂，對所得之鉛-酸電池進行與實施例1至3以及比較例1至3相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3, except that the ABS resin was changed to an ABS resin with a sand impact value of 25 kJ / m 2 as shown in Table 22. -Acid batteries perform the same tests and measurements as in Examples 1 to 3 and Comparative Examples 1 to 3.

在三氧化二銻之添加量為5質量份或更多之實施例16至18中，如表22所示，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。在三氧化二銻之添加量少於5質量份之比較例94至96中，所製造之電池殼的沙丕衝擊值高於實施例16至18且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Examples 16 to 18 in which the added amount of antimony trioxide is 5 parts by mass or more, as shown in Table 22, the manufactured battery case complies with the flammability rating of UL94V-0, and the sand impact value is 10kJ / m 2 or higher, and provides good processability. In Comparative Examples 94 to 96 in which the added amount of antimony trioxide was less than 5 parts by mass, the sand impact value of the manufactured battery case was higher than that of Examples 16 to 18 and provided good processability, but did not meet UL94V-0 Flammability rating.

<比較例97至101> <Comparative Examples 97 to 101>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨將ABS樹脂改成如表23所示沙丕衝擊值為25kJ/m2之ABS樹脂且溴化雙酚A之添加量改成13質量份，對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the ABS resin was changed to an ABS resin having a sand impact value of 25 kJ / m 2 and a brominated bisphenol as shown in Table 23. The added amount of A was changed to 13 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2.

在所有比較例97至101中，如表23所示，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In all Comparative Examples 97 to 101, as shown in Table 23, the sand impact impact value of the manufactured battery case was 10 kJ / m 2 or higher and provided good processability, but did not meet the flammability rating of UL94V-0.

<實施例19至30以及比較例102至109> <Examples 19 to 30 and Comparative Examples 102 to 109>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨如表24至27所示，將ABS樹脂改成沙丕衝擊值為25kJ/m2之ABS樹脂且溴化雙酚A之添加量分別改為15質量份、17質量份、23質量份、及25質量份，且對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that as shown in Tables 24 to 27, the ABS resin was changed to an ABS resin with a sand impact value of 25 kJ / m 2 and bromine. The addition amounts of bisphenol A were changed to 15 parts by mass, 17 parts by mass, 23 parts by mass, and 25 parts by mass, respectively. Test and measurement.

在三氧化二銻之添加量為5質量份或更多之實施例19至30中，如表24至27所示，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 19 to 30 in which the amount of antimony trioxide was 5 parts by mass or more, as shown in Tables 24 to 27, the manufactured battery cases met the flammability rating of UL94V-0, and the impact value of sand was 10kJ / m 2 or higher, and provides good processability.

在三氧化二銻之添加量少於5質量份之比較例102至109中，所製造之電池殼的沙丕衝擊值10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 102 to 109 in which the added amount of antimony trioxide is less than 5 parts by mass, the manufactured battery case has a sand impact value of 10 kJ / m 2 or higher and provides good processability, but does not meet UL94V-0. Flammability rating.

<比較例110至114> <Comparative Examples 110 to 114>

鉛-酸電池係以與實施例1至3以及比較例1及2相同方式製造，惟獨將ABS樹脂改成如表28所示沙丕衝擊值為25kJ/m2之ABS樹脂且溴化雙酚A之添加量改成27質量份，對所得之鉛-酸電池進行與實施例1至3以及比較例1及2相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except that the ABS resin was changed to an ABS resin with a sand impact value of 25 kJ / m 2 and a brominated bisphenol as shown in Table 28. The addition amount of A was changed to 27 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 1 to 3 and Comparative Examples 1 and 2.

在三氧化二銻之添加量如表28所示少於5質量份的比較例110及111中，所製造之電池殼的沙丕衝擊值為10kJ/m2或更高且提供良好加工性，但不符合UL94V-0之可燃性等級。 In Comparative Examples 110 and 111 in which the added amount of antimony trioxide is less than 5 parts by mass as shown in Table 28, the sand impact value of the manufactured battery case is 10 kJ / m 2 or higher and provides good processability. However, it does not meet the flammability rating of UL94V-0.

在三氧化二銻之添加量為5質量份或更多之比較例112至114中，所製造之電池殼符合UL94V-0之可燃性等級且提供良好加工性，但沙丕衝擊值低於10kJ/m2。 In Comparative Examples 112 to 114 in which the added amount of antimony trioxide is 5 parts by mass or more, the manufactured battery case complies with the flammability rating of UL94V-0 and provides good processability, but the sand impact value is less than 10kJ / m 2 .

接著，將雙硬脂醯胺之添加量改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行測試。 Next, the amount of distearylamine was changed to 0 parts by mass (without adding stearylamine), 0.1 parts by mass, 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid The battery is tested.

<實施例31至42以及比較例115至117> <Examples 31 to 42 and Comparative Examples 115 to 117>

以與實施例1至3相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表29至31所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例1至3相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 1 to 3, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine) as shown in Tables 29 to 31, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 1 to 3.

在如表29至31所示不添加雙硬脂醯胺之比較例115至117中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 115 to 117 without the addition of distearylamine as shown in Tables 29 to 31, the manufactured battery cases conform to the flammability rating of UL94V-0 and the sand impact value is 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例31至42中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 31 to 42 in which bisstearylamine was added, the manufactured battery cases conformed to the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

<實施例43至54以及比較例118至120> <Examples 43 to 54 and Comparative Examples 118 to 120>

以與實施例4至6相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表32至34所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例4至6相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 4 to 6, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine) as shown in Tables 32 to 34, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 4 to 6.

在如表32至34所示不添加雙硬脂醯胺之比較例118至120中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 118 to 120 without the addition of distearylamine as shown in Tables 32 to 34, the manufactured battery cases meet the flammability rating of UL94V-0 and the sand impact value is 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例43至54中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 43 to 54 in which bisstearylamine was added, the manufactured battery cases met the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

<實施例55至66以及比較例121至123> <Examples 55 to 66 and Comparative Examples 121 to 123>

以與實施例13至15相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表35至37所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例13至15相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 13 to 15, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine) as shown in Tables 35 to 37, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 13 to 15.

在如表35至37所示不添加雙硬脂醯胺之比較例121至123中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 121 to 123 without the addition of distearylamine as shown in Tables 35 to 37, the manufactured battery cases meet the flammability rating of UL94V-0 and the sand impact value is 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例55至66中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 55 to 66 in which distearylamine was added, the manufactured battery cases conformed to the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

<實施例67至78以及比較例124至126> <Examples 67 to 78 and Comparative Examples 124 to 126>

以與實施例16至18相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表38至40所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例16至18相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 16 to 18, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine) as shown in Tables 38 to 40, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 16 to 18.

在如表38至40所示不添加雙硬脂醯胺之比較例124至126中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 124 to 126 without the addition of distearylamine as shown in Tables 38 to 40, the manufactured battery cases meet the flammability rating of UL94V-0 and the sand impact value is 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例67至78中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 67 to 78 in which distearylamine was added, the manufactured battery cases conformed to the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

<實施例79至90以及比較例127至129> <Examples 79 to 90 and Comparative Examples 127 to 129>

以與實施例19至21相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表41至43所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例19至21相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 19 to 21, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine), as shown in Tables 41 to 43, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 19 to 21.

在如表41至43所示不添加雙硬脂醯胺之比較例127至129中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 127 to 129 without the addition of distearylamine as shown in Tables 41 to 43, the manufactured battery cases met the flammability rating of UL94V-0 and the sand impact value was 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例79至90中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 79 to 90 in which distearylamine was added, the manufactured battery cases conformed to the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

<實施例91至102以及比較例130至132> <Examples 91 to 102 and Comparative Examples 130 to 132>

以與實施例28至30相同方式製造鉛-酸電池，惟獨將雙硬脂醯胺之添加量如表44至46所示改成0質量份(不添加雙硬脂醯胺)、0.1質量份、0.2質量份、0.4質量份、及0.5質量份，且對所得之鉛-酸電池進行與實施例28至30相同的測試及測量。 Lead-acid batteries were manufactured in the same manner as in Examples 28 to 30, except that the amount of bisstearylamine was changed to 0 parts by mass (without adding stearylamine) as shown in Tables 44 to 46, and 0.1 parts by mass , 0.2 parts by mass, 0.4 parts by mass, and 0.5 parts by mass, and the obtained lead-acid batteries were subjected to the same tests and measurements as those of Examples 28 to 30.

在如表44至46所示不添加雙硬脂醯胺之比較例130至132中，所製造之電池殼符合UL94V-0之可燃性等級且沙丕衝擊值為10kJ/m2或更高，但未提供良好加工性。 In Comparative Examples 130 to 132 in which no distearylamine is added as shown in Tables 44 to 46, the manufactured battery cases meet the flammability rating of UL94V-0 and the sand impact value is 10kJ / m 2 or higher. However, it does not provide good processability.

在添加雙硬脂醯胺之實施例91至102中，所製造之電池殼符合UL94V-0之可燃性等級，沙丕衝擊值為10kJ/m2或更高，且提供良好加工性。 In Examples 91 to 102 in which bisstearylamine was added, the manufactured battery cases conformed to the flammability rating of UL94V-0, the sand impact value was 10 kJ / m 2 or higher, and good processability was provided.

根據本發明，用於鉛-酸電池之電池殼係由含有沙丕衝擊值為20kJ/m2或更高之ABS樹脂(作為主要組分)以及添加至其中之阻燃劑的樹脂材料所形成。如此，可獲得獲致符合UL94V-0之可燃性等級之高抗燒性且沙丕衝擊值為10kJ/m2或更高的用於鉛-酸電池之電池殼。 According to the present invention, a battery case for a lead-acid battery is formed of a resin material containing an ABS resin having a sand impact value of 20 kJ / m 2 or higher (as a main component) and a flame retardant added thereto. . In this way, it is possible to obtain a battery case for a lead-acid battery having a high burn resistance that meets the flammability level of UL94V-0 and a sand impact value of 10 kJ / m 2 or higher.

雖然已參照實例實施態樣說明本發明之某些特徵，但該等說明無意構成限制概念。對本發明所屬技術領域中具通常知識者而言顯見之對該等實例實施態樣之各種修改、以及本發明之其他實施態樣，係視為落於本發明之精神及範疇內。 Although certain features of the invention have been described with reference to example implementations, these descriptions are not intended to be a limiting concept. Various modifications of the implementation modes apparent to those skilled in the art to which the present invention pertains and other implementation aspects of the present invention are deemed to fall within the spirit and scope of the present invention.

Claims (4)

一種用於鉛-酸電池之電池殼，其係由包括作為主要組分之沙丕衝擊值(Charpy impact value)為20kJ/m2或更高之ABS樹脂以及含有阻燃劑之添加劑的樹脂材料所模製，其中以每100質量份之該ABS樹脂計，該添加劑係含有15至25質量份之溴化雙酚A、5質量份或更多之三氧化二銻、及0.1質量份或更多之雙硬脂醯胺(bis-stearic acid amide)，以使該電池殼符合UL94V-0之可燃性等級(flammability class)且該電池殼之沙丕衝擊值為10kJ/m2或更高。A battery case for a lead-acid battery is composed of a resin material including an ABS resin having a Charpy impact value of 20 kJ / m 2 or higher as a main component and a flame retardant-containing additive. Molded in which, based on 100 parts by mass of the ABS resin, the additive contains 15 to 25 parts by mass of brominated bisphenol A, 5 parts by mass or more of antimony trioxide, and 0.1 parts by mass or more Mostly bis-stearic acid amide, so that the battery case meets the flammability class of UL94V-0 and the sand impact value of the battery case is 10kJ / m 2 or higher. 如申請專利範圍第1項之用於鉛-酸電池之電池殼，其中作為該樹脂材料之主要組分的ABS樹脂的沙丕衝擊值為25kJ/m2或更高。For example, the battery case for lead-acid batteries in the first scope of the patent application, wherein the sand impact value of the ABS resin as the main component of the resin material is 25 kJ / m 2 or higher. 一種鉛-酸電池，其包含如申請專利範圍第1或2項之用於鉛-酸電池的電池殼。A lead-acid battery includes a battery case for a lead-acid battery as described in claim 1 or 2. 一種用於鉛-酸電池之電池殼的樹脂材料，其中以每100質量份之沙丕衝擊值為20kJ/m2或更高的ABS樹脂計，添加至該樹脂材料之添加劑係含有15至25質量份之溴化雙酚A、5質量份或更多之三氧化二銻、及0.1質量份或更多之脂肪醯胺，該脂肪醯胺為雙硬脂醯胺。A resin material for a battery case of a lead-acid battery, wherein an additive added to the resin material based on a sand impact value of 20 kJ / m 2 or higher per 100 parts by mass contains 15 to 25 Parts by mass of brominated bisphenol A, 5 parts by mass or more of antimony trioxide, and 0.1 parts by mass or more of fatty ammonium, which is stearylamine.
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