CN105122495B - 电池容器用包装材用聚氨酯接着剂、电池用包装材、电池用容器及电池 - Google Patents
电池容器用包装材用聚氨酯接着剂、电池用包装材、电池用容器及电池 Download PDFInfo
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- CN105122495B CN105122495B CN201480009913.8A CN201480009913A CN105122495B CN 105122495 B CN105122495 B CN 105122495B CN 201480009913 A CN201480009913 A CN 201480009913A CN 105122495 B CN105122495 B CN 105122495B
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- acrylic acid
- outer layer
- polyurethane adhesives
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明提供一种在长期耐久试验后还可维持大的接着强度、可形成成型性优异的电池用包装材的接着剂、电池用包装材、电池用容器及电池。本发明的电池用包装材用聚氨酯接着剂含有主剂与硬化剂,主剂包含数量平均分子量为10,000~100,000、且羟值为1mgKOH/g~100mgKOH/g的丙烯酸系多元醇(A),相对于源自丙烯酸系多元醇(A)的羟基,源自硬化剂中所含的芳香族异氰酸酯(B)的异氰酸酯基的当量比[NCO]/[OH]设为10~30。
Description
技术领域
本发明涉及一种用以形成电池用容器或电池封装(pack)的电池用包装材用聚氨酯接着剂。并且本发明涉及一种使用上述电池用包装材用聚氨酯接着剂而层叠的电池用包装材。而且本发明涉及一种将上述电池用包装材成型而成的电池用容器、及使用上述电池用容器而成的电池。
背景技术
由于移动电话、可携型计算机等电子设备的急速成长,轻量且小型的锂离子电池等二次电池的需求增大。作为二次电池的外包装体,之前使用金属制罐,但就轻量化或生产性的观点而言,将塑料膜或铝箔等层叠而成的包装材正成为主流。
作为最简易的包装材,可列举:如图1所示的自外层侧起依序包含外层侧树脂膜层(11)、外层侧接着剂层(12)、金属箔层(13)、内层侧接着剂层(14)及含有热密封层等的内面层(15)的层叠体。作为电池用容器,例如如图2所示,有以外层侧树脂膜层(11)构成凸面、内面层(15)构成凹面的方式将上述包装材成型(伸拉成型加工、突出成型加工等)的。电池可通过在电池用容器的凹面侧封入电极或电解液等进行密封而制造。
作为电池用包装材,揭示有以下的构成:在外层侧层叠耐热性树脂延伸膜层、在内层侧层叠热塑性树脂未延伸膜层、在这些两膜之间层叠铝箔层的电池用容器包材中,热塑性树脂未延伸膜层与铝箔层经由含有具有羧基的聚烯烃树脂、及多官能异氰酸酯化合物而成的接着剂层而接着(专利文献1)。
另外,揭示有电子零件盒用包材,其自外侧起依序需要耐热性树脂延伸膜层、铝箔层及热塑性树脂未延伸膜层,在铝箔层与热塑性树脂未延伸膜层之间设置丙烯酸系聚合物层而成(专利文献2)。
另外揭示,在锂电池用外包装材中,作为在延伸聚酰胺膜等基材层与铝箔层之间所用的接着剂,在聚酯多元醇或丙烯酸系多元醇等主剂中,使用异氰酸酯化合物作为硬化剂,NCO/OH较优选为1~10,更优选为2~5(专利文献3)。此外,在专利文献4~专利文献6中揭示电池用外包装材。
[现有技术文献]
[专利文献]
[专利文献1]日本专利特开2010-92703号公报
[专利文献2]日本专利特开2002-187233号公报
[专利文献3]日本专利特开2012-124067号公报第25段
[专利文献4]日本专利特开2002-002511号公报
[专利文献5]国际公开第2008/093778号
[专利文献6]国际公开第2009/041077号
发明内容
发明要解决的课题
近年来,随着在车载或家庭蓄电等的用途扩大,而对二次电池要求大容量化,并对电池用包装材要求良好的成型性。
另外,车载或家庭蓄电用途的二次电池设置于室外,而进一步要求长期的耐用年数,因此要求在长期耐久试验后还可维持包装材的各塑料膜或金属箔等层间的接着强度,而且外观无异常。
本发明是鉴于上述背景而成的,课题是提供一种具有优异的成型性、在长期耐久性试验后层间的接着强度也高、且外观性优异的电池、电池用容器、电池用包装材及电池用包装材用聚氨酯接着剂。
解决问题的技术手段
本发明是鉴于上述课题而成的,涉及一种电池用包装材用聚氨酯接着剂,其含有主剂与硬化剂,且上述主剂包含数量平均分子量为10,000~100,000、且羟值为1mgKOH/g~100mgKOH/g的丙烯酸系多元醇(A),相对于源自丙烯酸系多元醇(A)的羟基,源自上述硬化剂中所含的芳香族聚异氰酸酯(B)的异氰酸酯基的当量比[NCO]/[OH]为10~30。
本发明的电池用包装材用聚氨酯接着剂较优选为丙烯酸系多元醇(A)的玻璃化温度(Tg)为-20℃~30℃。
另外,本发明的电池用包装材用聚氨酯接着剂较优选为进一步含有:选自由硅烷偶合剂(C)、及磷酸或磷酸系化合物(D)所组成的组群的至少一种添加剂。
另外,本发明涉及一种电池用包装材,其自外层起依序需要外层侧树脂膜层、外层侧接着剂层、金属箔层、内层侧接着剂层、内面层,其中,上述外层侧接着剂层利用上述本发明的电池用包装材用聚氨酯接着剂而形成。
本申请发明的电池用包装材较优选为上述外层侧树脂膜层为聚酰胺膜或/和聚酯膜,上述内面层为聚烯烃系膜。
而且,本发明涉及一种电池用容器,其由上述电池用包装材成型而成,且外层侧树脂膜层构成凸面,内面层构成凹面。
而且,本发明涉及一种电池,其使用上述电池用容器而成。
发明的效果
根据本发明,会发挥出如下的优异效果:可提供具有优异的成型性、在长期耐久性试验后层间的接着强度也高、且外观性优异的电池、电池用容器、电池用包装材及电池用包装材用聚氨酯接着剂。
附图说明
图1是表示本发明的电池用包装材的一个形态的示意性剖面图。
图2是本发明的电池用容器的一个形态(托盘状)的示意性立体图。
符号的说明
(11):外层侧树脂膜层
(12):外层侧接着剂层
(13):金属箔层
(14):内层侧接着剂层
(15):内面层
具体实施方式
以下,对本发明的实施形态进行详细地说明。另外,在本说明书中,“任意的数A~任意的数B”的记载是指数A及大于数A的范围、且数B及小于数B的范围。
本发明的聚氨酯接着剂用于形成用以获得电池用容器的电池用包装材。电池用容器的形状并无特别限定,除了如图2所示的托盘状的外,可例示:筒状(圆筒、四角筒、椭圆筒等)的。这些电池用容器可将平的状态的电池用包装材进行成型加工而得。电池用容器的内侧、即与电解液接触的面为内面层(15)。作为内面层(15)的较优选的例子,可列举热密封层。通过使用热密封层,而使凸缘部的内面层(15)、与构成另外电池用包装材的内面层(15)或另外电池用容器的凸缘部的内面层(15)对向、接触,并加热,由此可使内面层(15)彼此熔接,并封入电解液。内面层在不脱离本发明的主旨的范围内并无限定,可例示聚烯烃系膜作为较优选的例子。
电池用容器具备金属箔(13)。在电池用容器中,通常以金属箔(13)为界将靠近电解液之侧称为“内侧”,将内侧的层称为“内层”,将远侧称为“外侧”,将外侧的层称为“外层”。因此,在形成电池用容器的预定的电池用包装材中,也以金属箔(13)为界将位置靠近电解液的预定之侧称为“内侧”,将内侧的层称为“内层”,将位置远离的预定之侧称为“外侧”,将外侧的层称为“外层”。
本发明的聚氨酯系接着剂适合于用以将外层侧树脂膜层(11)与金属箔层(13)层叠(贴合)的用途。
本发明的聚氨酯系接着剂是使用主剂与硬化剂的。可为在使用时将主剂与硬化剂混合的所谓的二液混合型接着剂,也可为预先混合主剂与硬化剂的一液型接着剂。而且,还可为在使用时将多种主剂和/或多种硬化剂混合的类型。
本发明的聚氨酯系接着剂中,主剂是具有羟基的多元醇成分,并含有丙烯酸系多元醇(A)。多元醇成分在满足本发明的目的、效果的范围内可进一步包含丙烯酸系多元醇(A)以外的多元醇。
丙烯酸系多元醇(A)较优选为使用:含有羟基的单(甲基)丙烯酸酯单体、与不含有羟基的单(甲基)丙烯酸酯单体的共聚物。含有羟基的单(甲基)丙烯酸酯单体是在1分子中含有1个(甲基)丙烯酰基与1个以上羟基的单体,且除了一元醇外,还包括二元醇的单(甲基)丙烯酸酯单体等。
具有1个羟基的单(甲基)丙烯酸酯单体例如可通过使二元醇与(甲基)丙烯酸反应而得。作为具体例,可列举:(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸3-羟基丙酯、(甲基)丙烯酸2-羟基丁酯、丙烯酸4-羟基丁酯(商品名4HBA、三菱化学公司制造)、甲基丙烯酸4-羟基丁酯、丙烯酸α-羟基甲基乙酯、丙烯酸α-羟基甲酯、己内酯改性羟基(甲基)丙烯酸酯(商品名普拉赛尔(PLACCEL)F系列、大赛璐化学工业(DaicelChemical industries)公司制造)、(聚)乙二醇单(甲基)丙烯酸酯。
而且,也可利用如(甲基)丙烯酸2,3-二羟基丙酯等那样的具有2个羟基的单(甲基)丙烯酸酯单体。例如可使三元醇与(甲基)丙烯酸反应而得。
作为单(甲基)丙烯酸酯单体,可列举:(甲基)丙烯酸环己酯、(甲基)丙烯酸甲基环己酯、(甲基)丙烯酸第三丁基环己酯、(甲基)丙烯酸环十二烷基酯等含有环烷基的单体,丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸第三丁酯、丙烯酸第二丁酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸异戊酯、丙烯酸2-乙基己酯、丙烯酸异癸酯、丙烯酸十三烷基酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸正月桂酯、丙烯酸苄酯、丙烯酸二环戊酯、丙烯酸正硬脂酯、丙烯酸异硬脂酯、丙烯酸异冰片酯、丙烯酸2-(乙酰乙酰氧基)乙酯、丙烯酸苯氧基乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸异戊酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸异癸酯、甲基丙烯酸十三烷基酯、甲基丙烯酸正辛酯、甲基丙烯酸异辛酯、甲基丙烯酸正月桂酯、甲基丙烯酸苄酯、甲基丙烯酸二环戊酯、甲基丙烯酸正硬脂酯、甲基丙烯酸异硬脂酯、甲基丙烯酸异冰片酯、甲基丙烯酸2-乙酰乙酰氧基乙酯(商品名AAEM、伊士曼(Eastman))、甲基丙烯酸苯氧基乙酯等。而且可使用:(甲基)丙烯酸、顺丁烯二酸、顺丁烯二酸酐等含有羧基的单体、或其酐,或苯乙烯等乙烯系单体。
作为丙烯酸系多元醇(A)的分子量,数量平均分子量较优选为10,000~100,000,更优选为20,000~70,000。
在工业上生产电池用包装材时,将长条状态的卷取成卷状。并且,为了使卷取成卷状的层叠体中的接着剂层充分地硬化,而在维持为高温的仓库中进行数天老化。
通过将丙烯酸系多元醇(A)的数量平均分子量设为10,000以上,而可提高老化前或硬化中途所存在的接着剂层的凝聚力,并可抑制、防止外观不良等加工异常(卷取状态下产生偏移或隆起)的产生。而且通过将丙烯酸系多元醇(A)的数量平均分子量设为10,000以上,而可抑制、防止硬化涂膜的脆化,并可确保基材与接着剂间的剥离应力松弛,还可抑制、防止因层叠强度的降低或接着力不足引起的隆起的产生。
另一方面,通过将丙烯酸系多元醇(A)的数量平均分子量设为100,000以下,而可确保在稀释溶剂中的溶解性,并可使接着剂涂敷时的粘度为适度的范围,而确保涂敷性。另外认为,涂敷接着剂的硬化初始阶段的干燥涂膜通过丙烯酸系分子链的相互缠绕,而结构粘性变高,在侧链所具有的羟基的自由度降低,而阻碍丙烯酸系多元醇(A)中的羟基与后述的硬化剂中的异氰酸酯基的反应。通过将丙烯酸系多元醇(A)的数量平均分子量设为100,000以下,而抑制硬化初始阶段的丙烯酸系分子链的相互缠绕,并抑制羟基与异氰酸酯基的反应阻碍,由此可确保充分的氨酯交联度,并获得成型性优异的包装材。
丙烯酸系多元醇(A)的数量平均分子量是通过凝胶渗透色谱法(Gel PermeationChromatography,GPC)而得的聚苯乙烯换算的值。例如,将管柱(昭和电工公司制造的KF-805L、KF-803L、及KF-802)的温度设为40℃,使用四氢呋喃(tetrahydrofuran,THF)作为洗脱液,将流速设为0.2mL/min,将检测设为折射率(Refractive Index,RI),将试样浓度设为0.02%,并使用聚苯乙烯作为标准试样而进行测定。本发明的数量平均分子量记载通过上述方法而测定的值。
丙烯酸系多元醇(A)的羟值为1mgKOH/g~100mgKOH/g,较优选为1mgKOH/g~50mgKOH/g,更优选为1mgKOH/g~15mgKOH/g。若羟值超过100mgKOH/g,则丙烯酸系多元醇(A)与作为硬化剂而含有的芳香族异氰酸酯(B)的交联密度变得过高,而与外层侧树脂膜层的接着力降低,并且成型性也降低。
通过丙烯酸系多元醇(A)的羟值为上述范围,而外层侧树脂膜层及金属箔层的接着强度变得良好,而且丙烯酸系多元醇(A)与硬化剂中所含的芳香族异氰酸酯(B)形成恰当的交联密度,由此获得良好的成型性。
另外,丙烯酸系多元醇(A)的玻璃化温度较优选为-20℃~30℃的范围,更优选为0℃~15℃的范围。
通过丙烯酸系多元醇(A)的玻璃化温度为上述范围,而充分具有保持刚层叠后的接着强度的初始粘性,并获得成型性或成型物的耐湿热性优异的成型物。
丙烯酸系多元醇(A)的玻璃化温度通过示差扫描热量仪(Differential ScanningCalorimeter,DSC)测定而求出。具体而言,将约10mg的试样冷却至-100℃后,以10℃/min升温而获得DSC图表,并根据该DSC图表求出玻璃化温度。在丙烯酸系多元醇(A)溶解于有机溶剂时,进行干燥后以相同的方式求出玻璃化温度。
作为主剂所含的多元醇成分,还可并用丙烯酸系多元醇(A)以外的多元醇。例如可例示:乙二醇、三羟甲基丙烷等低分子多元醇,及聚醚多元醇,聚碳酸酯多元醇,聚烯烃多元醇,聚酯多元醇。另外可列举:使这些单独或并用2种以上与有机异氰酸酯反应而得的聚氨酯多元醇等。丙烯酸系多元醇(A)以外的多元醇可在不对接着强度或成型性造成不良影响的程度下使用。
本发明的聚氨酯接着剂包含芳香族聚异氰酸酯(B)作为硬化剂。芳香族聚异氰酸酯(B)可为利用有机溶剂稀释聚异氰酸酯而成的状态的,也可为未稀释的状态的。
作为芳香族聚异氰酸酯(B),可列举:间苯二异氰酸酯、对苯二异氰酸酯、4,4'-二苯基二异氰酸酯、1,5-萘二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯或2,6-甲苯二异氰酸酯或其混合物、4,4'-甲苯胺二异氰酸酯、联茴香胺二异氰酸酯、4,4'-二苯醚二异氰酸酯等芳香族二异氰酸酯;
三苯基甲烷-4,4',4”-三异氰酸酯、1,3,5-三异氰酸酯苯、2,4,6-三异氰酸酯甲苯等有机三异氰酸酯,4,4'-二苯基二甲基甲烷-2,2'-5,5'-四异氰酸酯等有机四异氰酸酯等聚异氰酸酯单体;
由上述聚异氰酸酯单体衍生的二聚物、三聚物、缩二脲、脲基甲酸酯,由二氧化碳与上述聚异氰酸酯单体而得的具有2,4,6-噁二嗪三酮环的聚异氰酸酯;
或乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、3,3'-二羟甲基丙烷、环己烷二甲醇、二乙二醇、三乙二醇、二丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇等分子量小于200的低分子多元醇与上述聚异氰酸酯单体加成而得的加成物;
或分子量为200~20,000的聚酯多元醇、聚醚酯多元醇、聚酯酰胺多元醇、聚己内酯多元醇、聚戊内酯多元醇、丙烯酸系多元醇、聚碳酸酯多元醇、聚羟基烷烃、蓖麻油、聚氨酯多元醇等与上述聚异氰酸酯单体加成而得的加成物等。
其中,就包装材的生产性及成型性的观点而言,更优选为由4,4'-二苯基甲烷二异氰酸酯、及2,4-甲苯二异氰酸酯或2,6-甲苯二异氰酸酯衍生的有机聚异氰酸酯。
本发明的聚氨酯接着剂中,相对于主剂中所含的丙烯酸系多元醇(A)所具有的羟基,源自硬化剂中所含的芳香族异氰酸酯(B)的异氰酸酯基的当量比[NCO]/[OH]为10~30,较优选为15~25。通过相对于羟基1摩尔,而将芳香族异氰酸酯基设为10摩尔以上,而可形成充分的交联密度的接着剂层,并可获得成型性优异的包装体。另一方面,通过相对于羟基1摩尔,而将芳香族异氰酸酯基设为30摩尔以下,而直至硬化结束为止不需要长时间,并可获得层叠强度优异的包装体。而且就卫生性、经济性的方面而言,也较优选为将芳香族异氰酸酯基设为30摩尔以下。
一般认为,通过当量比为上述的范围内,通过芳香族异氰酸酯基彼此利用脲键的自交联、及利用一部分芳香族异氰酸酯与水分的反应的末端胺化,而可形成不但具有对金属箔层的牢固的接着性而且一并具有需要高的杨氏模量(Young Modulus)的成型性的涂膜。
就提高对于金属箔等金属系原材料的接着强度的观点而言,本发明的聚氨酯接着剂较优选为包含硅烷偶合剂(C)。
作为硅烷偶合剂(C),例如可列举:乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷等具有乙烯基的三烷氧基硅烷;3-氨基丙基三乙氧基硅烷、N-(2-氨基乙基)3-氨基丙基三甲氧基硅烷等具有氨基的三烷氧基硅烷;3-缩水甘油氧基丙基三甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷等具有缩水甘油基的三烷氧基硅烷。这些分别可单独使用,或者可任意地组合2种以上而使用。
相对于多元醇成分的固体成分100质量份,硅烷偶合剂(C)的添加量较优选为0.1质量份~5质量份,更优选为0.5质量份~3质量份。通过添加上述范围的硅烷偶合剂(C),而可提高对于金属箔的接着强度。另外,硅烷偶合剂(C)较优选为与丙烯酸系多元醇(A)一起包含在主剂中。
就提高对于金属箔等金属系原材料的接着强度的观点而言,本发明所使用的聚氨酯接着剂较优选为包含磷酸或磷酸系化合物(D)。另外,磷酸或磷酸系化合物(D)较优选为与丙烯酸系多元醇(A)一起包含在主剂中。
在磷酸或磷酸系化合物(D)中,作为磷酸,只要为具有至少一个游离的氧酸的即可,例如可列举:次磷酸(hypophosphorous acid)、亚磷酸、正磷酸、低磷酸(hypophosphoric acid)等磷酸类,偏磷酸、焦磷酸、三聚磷酸、聚磷酸、超磷酸等缩合磷酸类。另外,作为磷酸的衍生物的磷酸系化合物可列举:使上述磷酸在残留至少一个游离的氧酸的状态下与醇类部分地酯化的等。作为这些醇,可列举:甲醇、乙醇、乙二醇、甘油等脂肪族醇,苯酚、二甲苯酚、对苯二酚、邻苯二酚、间苯三酚等芳香族醇等。磷酸或磷酸系化合物(D)能以1种使用,也能以任意的组合而组合2种以上来使用。磷酸或磷酸系化合物(D)的添加量以接着剂的固体成分为基准较优选为0.01质量%~10质量%,更优选为0.05质量%~5质量%,特别优选为0.05质量%~1质量%。
此外,作为接着剂用途,可在主剂、或硬化剂中调配公知的添加剂。例如可使用反应促进剂。例如可列举:二乙酸二丁基锡、二月桂酸二丁基锡、二月桂酸二辛基锡、二顺丁烯二酸二丁基锡等金属系催化剂;1,8-二氮杂双环(5,4,0)十一碳烯-7、1,5-二氮杂双环(4,3,0)壬烯-5、6-二丁基氨基-1,8-二氮杂双环(5,4,0)十一碳烯-7等三级胺;如三乙醇胺那样的反应性三级胺等,可使用选自这些的组群的1种或2种以上的反应促进剂。
为了提高层叠外观,还可在主剂中调配公知的流平剂或消泡剂。作为流平剂,例如可列举:聚醚改性聚二甲基硅氧烷、聚酯改性聚二甲基硅氧烷、芳烷基改性聚甲基烷基硅氧烷、聚酯改性含有羟基的聚二甲基硅氧烷、聚醚酯改性含有羟基的聚二甲基硅氧烷、丙烯酸系共聚物、甲基丙烯酸系共聚物、聚醚改性聚甲基烷基硅氧烷、丙烯酸烷基酯共聚物、甲基丙烯酸烷基酯共聚物、卵磷脂等。
作为消泡剂,可列举:硅酮树脂、硅酮溶液、烷基乙烯醚与丙烯酸烷基酯及甲基丙烯酸烷基酯的共聚物等公知的。
本发明的电池用包装材例如可通过通常所用的方法而制造。
例如,使用本发明的聚氨酯接着剂将外层侧树脂膜层(11)与金属箔层(13)层叠,而获得中间层叠体。继而,可使用内层侧接着剂在中间层叠体的金属箔层(13)面层叠内面层(15)。
或者,使用内层侧接着剂将金属箔层(13)与内面层(15)层叠,而获得中间层叠体。继而,可使用本发明的聚氨酯接着剂,将中间层叠体的金属箔层(13)与外层侧树脂膜层(11)层叠。
为前者时,本发明的聚氨酯接着剂只要涂布在外层侧树脂膜层(11)或金属箔层(13)的任一层的基材的单面,使溶剂挥发后,在加热加压下在接着剂层上重叠另一基材,继而在常温或加温下老化,使接着剂层硬化即可。接着剂层量较优选为1g/m2~15g/m2左右。
后者的情形也相同,本发明的聚氨酯接着剂只要涂布在外层侧树脂膜层(11)或中间层叠体的金属箔层(13)面的任一层面上即可。
在将聚氨酯系接着剂涂敷在基材上时,为了将涂液调整为适度的粘度,而可在干燥步骤中在对基材无影响的范围内包含溶剂。
作为溶剂,可列举:丙酮、甲基乙基酮、甲基异丁基酮、环己酮等酮系化合物,乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乙酸甲氧基乙酯等酯系化合物,二乙醚、乙二醇二甲醚等醚系化合物,甲苯、二甲苯等芳香族化合物,戊烷、己烷等脂肪族化合物,二氯甲烷、氯苯、氯仿等卤化烃化合物,乙醇、异丙醇、正丁醇等醇类,水等。这些溶剂可单独使用,也可并用2种以上。
作为本发明中涂敷聚氨酯系接着剂的装置,可列举:缺角轮涂布机(commacoater)、干式贴合机、辊刀片涂布机、模涂机、辊涂机、棒涂机、凹版辊涂布机、逆辊涂布机、刮刀涂布机(blade coater)、凹版涂布机、微凹版涂布机等。
构成本发明的电池用外包装材的外层侧树脂膜层(11)并无特别限定,较优选为使用包含聚酰胺或聚酯的延伸膜。另外,可利用碳黑或氧化钛等颜料进行着色。另外,也可涂布用以赋予滑性或防止受伤或对于氢氟酸的防止腐蚀的涂布剂、或旨在创意设计性的油墨等。另外,也可预先层叠2层以上的膜。膜层的厚度并无特别限定,较优选为12μm~100μm。
构成本发明的电池用外包装材的金属箔层(13)的厚度并无特别限定,较优选为20μm~80μm。另外,较优选为在金属箔层表面进行利用磷酸盐、铬酸盐、氟化物、三嗪硫醇化合物、异氰酸酯化合物等的化成处理。通过实施化成处理,而可抑制因电池的电解液引起的金属箔层表面的腐蚀劣化。而且较优选为在化成处理表面上在200℃左右的高温下将酰胺树脂、丙烯酸系树脂、偶合剂等公知的金属处理剂烧附于金属,进行有机处理。通过实施有机处理,而使金属箔层与接着剂更牢固地接着,而可进一步抑制金属箔层与接着剂间的隆起。
构成本发明的电池用外包装材的内面层(15)并无特别限定,较优选为热密封层,较优选为包含选自由聚乙烯、聚丙烯、烯烃系共聚物、这些的酸改性物及离子聚合物所组成的组群的至少一种热塑性树脂的未延伸膜。膜的厚度并无特别限定,较优选为20μm~150μm。
形成构成本发明的电池用外包装材的内层侧接着剂层(14)的接着剂并无特别限定,较优选为金属箔层(13)与内面层(15)的接着强度不会因电池的电解液而降低的,可使用公知的接着剂。
例如,可利用凹版涂布机等将组合了聚烯烃树脂与多官能异氰酸酯的接着剂或组合了多元醇与多官能异氰酸酯的接着剂涂布在金属箔层上,使溶剂干燥,在加热加压下在接着剂层上重叠内面层(15),继而在常温或加温下老化并使金属箔层(13)与内面层(15)贴合。
或者,可利用T模挤出机将酸改性聚丙烯等接着剂熔融挤出至金属箔层(13)上而形成接着剂层,在上述接着剂层上重叠内面层(15),并使金属箔层(13)与内面层(15)贴合。
在外层侧接着剂层(12)及内层侧接着剂层(14)这两个需要老化时,可一并老化。另外,老化温度设为室温~90℃,由此在2天~2周(week)内完成硬化,而表现出成型性。
本发明的电池用容器可使用上述电池用外包装材,以外层侧树脂膜层(11)构成凸面、内面层(15)构成凹面的方式进行成型而得。
另外,本发明中所谓的“凹面”,是指在将平的状态的电池用包装材进行成型加工而形成如图2所示的托盘状时,具有内部可收纳电解液的凹陷的面,本发明中所谓的“凸面”,是指具有上述凹陷的面的自身背面。
根据本发明的电池用包装材,为了形成外层侧接着剂层,而使用本发明的聚氨酯接着剂,因此层间的接着强度优异,成型时可有效地防止膜的断裂,而有效地防止成型部的隆起的产生。另外,可提供在耐久性试验后,还可维持上述性能的电池用包装材。根据使用上述电池用包装材而成的电池用容器,而可提供可靠性优异的电池。
[实施例]
继而,列举实施例及比较例对本发明进行更具体地说明。实施例及比较例中的%全部是指质量%。
(丙烯酸系多元醇合成例)
在具备冷凝器、氮气导入管、滴液漏斗、及温度计的四口烧瓶中,投入乙酸乙酯100质量份,并升温至80℃。继而,自滴液漏斗历时2小时在四口烧瓶中滴加:预先混合丙烯酸正丁酯41.5质量份、甲基丙烯酸乙酯56.5质量份、丙烯酸1.0质量份、丙烯酸2-羟基乙酯1.0质量份、及偶氮双异丁腈0.4质量份而成的单体液。然后,反应1小时并添加偶氮双异丁腈0.04质量份,继而反应1小时后,进行冷却,添加乙酸乙酯而获得固体成分为50%的丙烯酸系多元醇溶液(A-1)。
除了根据聚合引发剂偶氮双异丁腈的添加量调节分子量、或更换单体组成以外,以相同的方式,利用表1所示的单体组成获得固体成分为50%的丙烯酸系多元醇溶液(A-2)~丙烯酸系多元醇溶液(A-12)。
另外,数量平均分子量、玻璃化温度如上所述,通过GPC及DSC而求出。
具体而言,数量平均分子量是将管柱(昭和电工公司制造的KF-805L、KF-803L、及KF-802)的温度设为40℃,使用THF作为洗脱液,并将流速设为0.2mL/min,将检测设为RI,将试样浓度设为0.02%,使用聚苯乙烯作为标准试样而求出。
另外,玻璃化温度是使用精工电子(Seiko Instruments)公司制造的DSC“RDC220”,在铝盘中秤取约10mg的试样,并设置于DSC装置中通过液氮冷却至-100℃后,以10℃/min升温而获得DSC图表,并根据该DSC图表求出。
另外,酸值、羟值通过以下方式而求出。
<酸值(Acid Value,AV)的测定>在共塞锥形瓶中精密地秤取试样(聚酯多元醇溶液)约1g,添加甲苯/乙醇(容量比:甲苯/乙醇=2/1)混合液100mL而溶解。在其中添加酚酞试剂作为指示剂,并保持30秒钟。然后,利用0.1N醇性氢氧化钾溶液进行滴定直至溶液呈现淡红色为止。酸值通过下式而求出(单位:mgKOH/g)。
酸值(mgKOH/g)=(5.611×p×F)/S
其中,S:试样的采集量(g)
p:0.1N醇性氢氧化钾溶液的消耗量(mL)
F:0.1N醇性氢氧化钾溶液的力价
<羟值(Hydroxyl Value,OHV)的测定>在共塞锥形瓶中精密地秤取试样(多元醇溶液)约1g,添加甲苯/乙醇(容量比:甲苯/乙醇=2/1)混合液100mL而溶解。继而准确地添加5mL的乙酰化剂(在吡啶中溶解乙酸酐25g,制成体积为100mL的溶液),并搅拌约1小时。在其中添加酚酞试剂作为指示剂,并持续30秒钟。然后,利用0.1N醇性氢氧化钾溶液进行滴定直至溶液呈现淡红色为止。
羟值通过下式而求出(单位:mgKOH/g)。
羟值(mgKOH/g)=[{(q-p)×F×28.05}/S]+D
其中,S:试样的采集量(g)
p:0.1N醇性氢氧化钾溶液的消耗量(mL)
q:空实验的0.1N醇性氢氧化钾溶液的消耗量(mL)
F:0.1N醇性氢氧化钾溶液的力价
D:酸值(mgKOH/g)
[主剂的制造]实施例1~实施例7、实施例9、实施例12、实施例13与比较例1~比较例5中,仅使用丙烯酸系多元醇溶液(A-1)~丙烯酸系多元醇溶液(A-7)、丙烯酸系多元醇溶液(A-10)~丙烯酸系多元醇溶液(A-12),实施例8中添加硅烷偶合剂(KBM-403)与磷酸,实施例10与实施例11中,添加硅烷偶合剂获得主剂。
(硬化剂(B)的制造)
硬化剂B1:将利用乙酸乙酯稀释4,4'-二苯基甲烷二异氰酸酯的三羟甲基丙烷改性体(三羟甲基丙烷(Trimethylolpropane,TMP)加合物改性体)而制成固体成分为70%的树脂溶液的设为硬化剂B1。硬化剂B1的NCO%为10.0%。
硬化剂B2:将利用乙酸乙酯稀释甲苯二异氰酸酯的三羟甲基丙烷改性体(TMP加合物改性体)而制成固体成分为52.5%的树脂溶液的设为硬化剂B2。硬化剂B2的NCO%为9.0%。
硬化剂B3:将利用乙酸乙酯稀释六亚甲基二异氰酸酯的三羟甲基丙烷改性体(TMP加合物改性体)而制成固体成分为75%的树脂溶液的设为硬化剂B3。硬化剂B3的NCO%为12.5%。
(实施例1~实施例13、比较例1~比较例5)以表2所示的比例(g)调配主剂与硬化剂后,以非挥发成分为30%的方式添加乙酸乙酯,而获得聚氨酯接着剂。
相对于主剂中所含的羟值与酸值的合计的硬化剂中的异氰酸酯基的当量[NCO]/[OH]通过以下方式而求出。
[NCO]/[OH]
=[561×(硬化剂的NCO%)×(相对于主剂100g的硬化剂调配量(g))]/[(主剂的羟值的合计(mgKOH/g))×42×100]
(比较例6)主剂使用AD-502(东洋摩顿(Toyo-Morton)株式会社制造的聚酯多元醇),硬化剂使用CAT-10(东洋摩顿株式会社制造的异氰酸酯硬化剂),以表2所示的比例(g)调配主剂与硬化剂后,以非挥发成分为30%的方式添加乙酸乙酯,而获得聚氨酯接着剂。
(比较例7)投入间苯二甲酸83.2g、对苯二甲酸83.2g、乙二醇142.6g,在200℃~220℃下进行8小时酯化反应,将特定量的水馏出后,添加壬二酸188g,继而进行4小时酯化反应。将特定量的水馏出后,添加钛酸四异丁酯0.13g,并缓慢地减压,在1.3hPa~2.7hPa、230℃~250℃下进行3小时酯交换反应,而获得数量平均分子量为22,000、Tg-5℃的聚酯多元醇。
利用乙酸乙酯将该聚酯多元醇调整成非挥发成分为50%,而获得羟值为2.45mgKOH/g、酸值为0.1mgKOH/g的聚酯多元醇溶液(X)。
以表2所示的比例(g)调配该聚酯多元醇溶液(X)与硬化剂(B)后,以非挥发成分为30%的方式,添加乙酸乙酯而获得聚氨酯接着剂。
在厚度为40μm的铝箔的一个面上,以涂布量为5g/m2的量通过干式贴合机,涂布上述聚氨酯接着剂作为外层用接着剂,使溶剂挥发后,层叠厚度为30μm的延伸聚酰胺膜。
继而,在所得的层叠膜的铝箔的另一个面上,以涂布量为5g/m2的量通过干式贴合机涂布下述内层用接着剂,使溶剂挥发后,层叠厚度为30μm的未延伸聚丙烯膜,然后,在60℃下进行7天的硬化(老化),使外层用接着剂及内层用接着剂硬化而获得电池用包装材。
(内层用接着剂)
在容器中加入:顺丁烯二酸改性聚丙烯(在丙烯与乙烯的共聚物中接枝聚合顺丁烯二酸酐而成的改性聚丙烯树脂、熔解温度:67℃、酸值:13mgKOH/g):60质量份、作为粘着赋予剂的完全氢化C9树脂(软化点:140℃、无酸值):40质量份,利用甲苯/甲基乙基酮=8/2的混合溶剂进行稀释,并在50℃下加热搅拌3小时而获得主剂,将上述主剂与利用甲苯稀释六亚甲基二异氰酸酯的三聚物制成固体成分为50%溶液而得的硬化剂,以质量比计为主剂/硬化剂=100/10进行调配,以非挥发成分为30%的方式,添加甲苯而制成内层用接着剂。
根据下述评价法,对以上述方式而得的电池用包装材进行性能评价。
<耐湿热性试验前、后的层叠强度>将电池用包装材切割成200mm×15mm的大小,在温度为20℃、相对湿度为65%的环境下,使用拉伸试验机以负荷速度为300mm/分钟进行T型剥离试验。以各5个试验片的平均值表示延伸聚酰胺膜与铝箔间的剥离强度(N/15mm宽度)(耐湿热性试验前的层叠强度)。
另外,将电池用包装材放入85℃、85%RH环境的恒温恒湿槽中,静置168小时后,将电池用包装材自恒温恒湿槽取出,以与试验前相同的方式,测定层叠强度(耐湿热性试验后的层叠强度)。根据各剥离强度的平均值,进行以下4阶段的评价。
aa:6N/15mm以上(实用上优异)
a:4N/15mm以上、小于6N/15mm(实用区域)
b:2N/15mm以上、小于4N/15mm(实用下限)
c:小于2N/15mm
将以上结果一并表示于表3。
<成型性评价法>将电池用包装材切割成80mm×80mm的大小,并作为空白样品(被成型材、原材料)。对上述空白样品,以延伸聚酰胺膜成为外侧的方式,通过无成型高度限制的直模具进行突出而进行1阶段成型,并根据铝箔未产生断裂、且各层间未产生隆起的最大的成型高度评价成型性。
另外,所使用的模具的打孔机形状是一条边为30mm的正方形、圆角R2mm、打孔机肩R 1mm。所使用的模具的模具孔形状是一条边为34mm的正方形、模具孔圆角R 2mm、模具孔肩R:1mm,打孔机与模具孔的间隙(clearance)是单侧为0.3mm。由于上述间隙而产生与成型高度对应的倾斜。根据成型的高度,进行以下的4阶段的评价。
aa:6mm以上(实用上优异)
a:4mm以上、小于6mm(实用区域)
b:2mm以上、小于4mm(实用下限)
c:小于2mm
将以上的结果表示于表3。
<成型物的耐湿热性>将电池用包装材切割成60mm×60mm的大小,并作为空白样品(被成型材、原材料)。对上述空白样品,以延伸聚酰胺膜成为外侧的方式,通过无成型高度限制的直模具以成型高度为3mm进行突出而进行1阶段成型。将所得的30mm方形托盘放入至85℃、85%RH环境下的恒温恒湿槽中,并静置168小时。自恒温恒湿槽取出上述托盘,确认凸缘部与侧壁部的边界部附近的外观,并评价是否在延伸聚酰胺膜与铝箔之间产生隆起。
另外,所使用的模具的打孔机形状是一条边为30mm的正方形、圆角R2mm、打孔机肩R 1mm、模具肩R:1mm。
a:无隆起
c:产生隆起
将以上的结果一并表示于表3。
[表1]
n-BA:丙烯酸正丁酯、EMA:甲基丙烯酸乙酯、MMA:甲基丙烯酸甲酯、AA:丙烯酸、
HEA:丙烯酸2-羟基乙酯、4HBA:丙烯酸4-羟基丁酯
[表3]
根据表3的结果可知,通过使用包含数量平均分子量为10,000~100,000、且羟值为1mgKOH/g~100mgKOH/g的丙烯酸系多元醇(A),且在相对于源自丙烯酸系多元醇(A)的羟基、源自硬化剂中所含的芳香族聚异氰酸酯(B)的异氰酸酯基的当量比[NCO]/[OH]为10~30的范围内调配而成的电池用包装材用聚氨酯接着剂,而可提供耐湿热性试验前、后的层叠强度、成型性优异,在长期耐久性试验中,层间的接着强度也高,且外观性优异的电池用包装材。另外还可知,可由使用电池用包装材用聚氨酯接着剂的电池用包装材形成耐湿热性优异的成型物。
比较例1中,在耐湿热性试验前的层叠强度的方面,并不逊于实施例,但由于硬化剂的聚异氰酸酯为脂肪族聚异氰酸酯,因此虽然耐湿热试验后的层叠强度为实用水平内,但有降低的倾向,并且成型性与成型物的耐湿热性差。
比较例2中,相对于源自主剂中的多元醇(A)的羟基,芳香族聚异氰酸酯硬化剂中所含的异氰酸酯基的当量比过小,因此虽然耐湿热试验后的层叠强度为实用水平内,但有降低的倾向,并且成型性与成型物的耐湿热性差。
另外,比较例3中,由于丙烯酸系多元醇的数量平均分子量过小,因此耐湿热试验前后的层叠强度差。比较例4中,由于丙烯酸系多元醇的数量平均分子量过大,因此源自主剂的羟基与源自硬化剂的异氰酸酯基的反应受到阻碍,虽然成型性为实用水平内,但有降低的倾向,并且成型物的耐湿热性差。
另外,比较例5中,源自主剂中的多元醇(A)的羟基过多,而丙烯酸系多元醇(A)与芳香族聚异氰酸酯的交联密度变得过高,因此导致层叠强度降低。另外,虽然成型性或成型物的耐湿热性为实用水平内,但有降低的倾向。
另外,比较例6中,由于主剂为聚酯多元醇,因此会促进通过耐湿热试验的水解,而成形物的耐湿热性差。比较例7中还由于主剂为聚酯多元醇,根据相同的理由,成形物的耐湿热性差,而且成形性也差。另外,比较例6、比较例7中,有耐湿热试验后的层叠强度降低的倾向。
产业上的可利用性
本发明的聚氨酯接着剂可作为用于形成电池用容器或电池用封装的接着剂而广范围地应用。特别是,本发明的聚氨酯接着剂适合作为用于形成锂离子电池、锂离子聚合物电池、铅蓄电池、碱电池、氧化银-锌蓄电池、金属空气电池、多价阳离子电池、电容器(condenser)、电容器(capacitor)等二次电池用电池用容器或电池用封装的接着剂。本发明的聚氨酯接着剂是用于将相同或不同的原材料的被粘接体接合的,例如可较优选地用于塑料系原材料与金属系原材料的多层层叠体的接合。当然,也适合于塑料系原材料彼此、金属系原材料彼此的接合。使用本发明的接着剂而得的层叠物的成型性优异,环境耐性高,在室外暴露的条件也可抑制经时的接着强度的降低,可长期维持强的接着强度及外观形状。因此,还可用作:泡壳包装(Press Through Package,PTP)或钢板等需要成型性的层叠物、或防壁材、屋顶材、太阳电池面板材、窗材、室外地板材、照明保护材、汽车构件等建筑物等室外产业用途层叠物用的接着剂。
该发明主张基于2013年2月25日提出申请的日本专利申请案特愿2013-34957及2013年12月11日提出申请的日本专利申请案特愿2013-255982的优先权,并将其揭示的全部内容并入本文中。
Claims (7)
1.一种电池容器用包装材用聚氨酯接着剂,其含有主剂与硬化剂,且其特征在于:
所述主剂包含数量平均分子量为10,000~100,000、且羟值为1mgKOH/g~53mgKOH/g的丙烯酸系多元醇(A),
相对于源自丙烯酸系多元醇(A)的羟基,源自所述硬化剂中所含的芳香族聚异氰酸酯(B)的异氰酸酯基的当量比[NCO]/[OH]为11~30。
2.根据权利要求1所述的电池容器用包装材用聚氨酯接着剂,其中丙烯酸系多元醇(A)的玻璃化温度(Tg)为-20℃~30℃。
3.根据权利要求1或2所述的电池容器用包装材用聚氨酯接着剂,其中进一步含有选自由硅烷偶合剂(C)及磷酸或磷酸系化合物(D)所组成的组群的至少一种添加剂。
4.一种电池用包装材,其自外层起依序需要外层侧树脂膜层、外层侧接着剂层、金属箔层、内层侧接着剂层、内面层,其特征在于:所述外层侧接着剂层利用根据权利要求1至3中任一项所述的电池容器用包装材用聚氨酯接着剂而形成。
5.根据权利要求4所述的电池用包装材,其特征在于:所述外层侧树脂膜层为聚酰胺膜或/和聚酯膜,所述内面层为聚烯烃系膜。
6.一种电池用容器,其由自外层起依序需要外层侧树脂膜层、外层侧接着剂层、金属箔层、内层侧接着剂层、内面层的根据权利要求4或5所述的电池用包装材成型而成,且所述外层侧树脂膜层构成凸面,所述内面层构成凹面。
7.一种电池,其使用根据权利要求6所述的电池用容器而成。
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JP2016169318A (ja) * | 2015-03-13 | 2016-09-23 | 東洋インキScホールディングス株式会社 | 積層体用接着剤組成物 |
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WO2017135361A1 (ja) * | 2016-02-03 | 2017-08-10 | 凸版印刷株式会社 | 蓄電デバイス用外装材、及び蓄電デバイス用外装材の製造方法 |
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JP2020502319A (ja) * | 2016-12-15 | 2020-01-23 | アメリカ合衆国 | 要求に応じて分解する熱硬化性樹脂のためのシリル含有アルコールおよびアミン |
TWI749129B (zh) | 2016-12-20 | 2021-12-11 | 日商迪愛生股份有限公司 | 電池用包裝材料用接著劑、電池用包裝材料、電池用容器及電池 |
JP7033414B2 (ja) * | 2017-09-14 | 2022-03-10 | 昭和電工パッケージング株式会社 | 成形用包装材、蓄電デバイス用外装ケース及び蓄電デバイス |
CN109554136A (zh) * | 2018-09-28 | 2019-04-02 | 桑顿新能源科技有限公司 | 一种锂离子电池专用胶带及其应用 |
BR112021009932A2 (pt) * | 2018-11-22 | 2021-08-17 | Dow Global Technologies Llc | composição adesiva de poliuretano, processo, estrutura de filme laminado de compósito de múltiplas camadas, e, pacote |
CN110128986A (zh) * | 2019-05-22 | 2019-08-16 | 无锡风鹏新材料科技有限公司 | 一种用于锂电池铝塑膜的聚酯型复合胶 |
CN110819291B (zh) * | 2019-12-06 | 2022-04-15 | 中国乐凯集团有限公司 | 一种电池软包装用聚氨酯胶粘剂 |
US11342617B2 (en) | 2020-01-10 | 2022-05-24 | Ford Global Technologies, Llc | Urethane based adhesives for securing and sealing battery pack enclosure assemblies |
WO2021162059A1 (ja) * | 2020-02-10 | 2021-08-19 | 大日本印刷株式会社 | 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス |
JPWO2022009829A1 (zh) * | 2020-07-06 | 2022-01-13 | ||
CN111909649B (zh) * | 2020-07-24 | 2022-06-21 | 中国乐凯集团有限公司 | 胶粘剂、太阳能电池背板和太阳能电池 |
CN112708388B (zh) * | 2021-01-08 | 2022-08-12 | 中国乐凯集团有限公司 | 一种锂电池包装用胶黏剂 |
CN116888182A (zh) | 2021-03-12 | 2023-10-13 | 陶氏环球技术有限责任公司 | 层压复合薄膜结构 |
CN114369443B (zh) * | 2022-01-13 | 2023-09-26 | 中国乐凯集团有限公司 | 聚氨酯粘结剂及其应用 |
JP7439182B2 (ja) | 2022-07-28 | 2024-02-27 | 株式会社レゾナック・パッケージング | 電池用包装材 |
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JP3845273B2 (ja) * | 2000-10-13 | 2006-11-15 | 昭和電工パッケージング株式会社 | 電子部品ケース用包材 |
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US20100210745A1 (en) * | 2002-09-09 | 2010-08-19 | Reactive Surfaces, Ltd. | Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes |
JP4360139B2 (ja) * | 2003-08-11 | 2009-11-11 | 東亞合成株式会社 | 電池ケース用包装材料及びそれを用いて成形された電池ケース |
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EP2709186B1 (en) * | 2011-05-11 | 2016-10-19 | Toppan Printing Co., Ltd. | Cladding for lithium ion cell, lithium ion cell, and method for producing lithium ion cell |
JP5899822B2 (ja) * | 2011-11-04 | 2016-04-06 | 凸版印刷株式会社 | ガスバリア積層フィルムおよびその製造方法 |
JP5867019B2 (ja) * | 2011-11-25 | 2016-02-24 | 東洋インキScホールディングス株式会社 | 接着剤組成物及び太陽電池用裏面保護シート |
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US20150380695A1 (en) | 2015-12-31 |
JP5578269B1 (ja) | 2014-08-27 |
TWI622205B (zh) | 2018-04-21 |
CN105122495A (zh) | 2015-12-02 |
TW201448322A (zh) | 2014-12-16 |
JP2014185317A (ja) | 2014-10-02 |
KR20150119879A (ko) | 2015-10-26 |
WO2014129192A1 (ja) | 2014-08-28 |
KR101615514B1 (ko) | 2016-04-26 |
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