TWI553950B - 層合用接著劑、使用其之積層體、及二次電池 - Google Patents

層合用接著劑、使用其之積層體、及二次電池 Download PDF

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TWI553950B
TWI553950B TW104119341A TW104119341A TWI553950B TW I553950 B TWI553950 B TW I553950B TW 104119341 A TW104119341 A TW 104119341A TW 104119341 A TW104119341 A TW 104119341A TW I553950 B TWI553950 B TW I553950B
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polyolefin resin
solvent
laminate
adhesive
resin
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TW104119341A
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TW201613160A (en
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中村英美
松尾高年
神山達哉
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迪愛生股份有限公司
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Description

層合用接著劑、使用其之積層體、及二次電池
本發明係關於用以密封在二次電池中所使用之電解質的層合用接著劑、使用其之積層體、及二次電池。
以鋰離子電池為代表之二次電池係作成為在正極、負極及其間密封入電解液等的構成。又，作為為了將正極及負極的電導出至外部用之導線予以密封的密封袋，係可使用貼合有鋁箔等金屬箔或金屬蒸鍍層與塑膠的積層體。
對於該積層體，係要求作為二次電池所要求之防濕性、密封性、耐戳刺性、絕緣性、耐熱/耐寒性、耐腐蝕性等，其中，難以藉由低溫硬化來獲得不會溶解於電解質之耐電解質性。
例如，在專利文獻1中，已提案有：在積層體之最內層使用馬來酸改性聚烯烴樹脂，以相同馬來酸改性聚烯烴樹脂構成熱封部，藉以使密封信賴性提升的密封袋。馬來酸改性聚烯烴樹脂係因與金屬之接著性及熱 封性優異，一般係可當作為接著性樹脂來使用。然而，當作為如上所述電池之密封薄膜來使用時，雖顯示出在高溫下積層後的優異接著力，但是耐電解質性低，隨時間會產生層間剝離而無法當作密封薄膜來使用。
在專利文獻2中，記載著一種電池電解液密封薄膜用積層體或電池電極部保護薄膜用積層體，其係包含：金屬層；金屬層表面上所形成之表面處理層；及表面處理層上所形成之包括羧酸基或其衍生物經改性過之聚烯烴之接著性樹脂層。
在專利文獻3中，記載著一種包括(A)聚烯烴系樹脂與(B)環氧化植物油的接著性樹脂組成物，其中，該(A)聚烯烴系樹脂係具有由酸酐基、羧基及羧酸金屬鹽類所構成之群組所選出之至少1種官能基，該(B)環氧化植物油係具有2個以上環氧基且分子量為3000以下；相對於(A)成分100重量份之(B)成分的配合量為0.01~5重量份。
在專利文獻4中，記載著一種二次電池電極用黏合劑用樹脂組成物，其特徵為含有酸改性聚烯烴樹脂(A)及聚胺基甲酸酯樹脂(B)，相對於(A)100質量份，(B)為0.5~100質量份。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開平09-283101號公報
[專利文獻2]WO 2007017043號公報
[專利文獻3]日本特開平08-193148號公報
[專利文獻4]日本特開2010-277959號公報
就習知技術而言，係呈不知道有解決上述課題用之層合用接著劑，且不知道具備本發明要件之層合用接著劑的狀況。
於是，本發明之課題係在於提供一種先前所未有之層合接著劑，其係因溶劑安定性優異而提升塗敷性，藉以提供一種層合積層體用接著劑組成物、使用其之積層體、及二次電池，其中，該層合積層體用接著劑組成物係金屬層與塑膠層之接著性優異，滿足防濕性、耐熱性、絕緣性、耐久性等，甚至即便是依低溫熟成也可兼備耐電解質性，且隨時間不會產生層間剝離。
為了解決本發明之課題，本發明者等進行檢討後之結果係藉由如下層合用接著劑來解決上述課題，其中，該層合用接著劑係含有非氯系聚烯烴樹脂(A)、環氧化合物(B)、及以環狀烷烴化合物為必要成分且包括酯系溶劑或醇系溶劑之有機溶劑(C)，有機溶劑(C)係由依環狀烷烴化合物之質量份與其以外之溶劑之質量份的比率為1/1~20/1之範圍所構成者。
如根據本發明，則可提供一種層合積層體用接著劑組成物、使用其之積層體、及二次電池，其中， 該層合積層體用接著劑組成物係金屬層與塑膠層之接著性優異，滿足防濕性、耐熱性、絕緣性、耐久性等，甚至即便是於低溫熟成也可兼備耐電解質性，且隨時間不會產生層間剝離。
本發明係由如下項目所構成。
1.一種層合用接著劑，其係含有非氯系聚烯烴樹脂(A)、環氧化合物(B)、及以環狀烷烴化合物為必要成分且包括酯系溶劑或醇系溶媒之有機溶劑(C)，其中，有機溶劑(C)係環狀烷烴化合物之質量份與其以外之溶劑之質量份的比率以1/1~20/1之範圍所構成。
2.如1.之層合用接著劑，其中環狀烷烴化合物為甲基環己烷，酯系溶劑為乙酸乙酯，醇系溶媒為碳數1~4之脂肪族醇。
3.如1.或2.之層合用接著劑，其中該非氯系聚烯烴樹脂(A)係含有酸價為1~200mgKOH/g之改性聚烯烴樹脂或羥基價為1~200mgKOH/g之改性聚烯烴樹脂。
4.如1.至3.中任一項之層合用接著劑，其中環氧化合物(B)係以一分子中具有2個以上環氧基且一分子中具有1個以上羥基、重量平均分子量為3000以下之環氧化合物為必要成分。
5.如1.至4.中任一項之層合用接著劑，其中相對於該非氯系聚烯烴樹脂(A)100質量份，環氧化合物(B)係以 0.01~30質量份的比例來摻合。
6.如1.至5.中任一項之層合用接著劑，其可進一步含有熱塑性彈性體、黏著賦予劑、觸媒、磷酸化合物、三聚氰胺樹脂、矽烷偶合劑或反應性彈性體。
7.一種積層體，其係將如1.至6.中任一項之層合用接著劑使用在金屬層與聚烯烴樹脂層間而成。
8.一種二次電池，其係將如7.之積層體當作電解液密封薄膜或電極部保護薄膜來使用而成。
(非氯系聚烯烴樹脂(A))
本發明所使用之非氯系聚烯烴樹脂(A)係只要是不含有氯原子的非氯系聚烯烴樹脂(A)即可，可使用以下的聚烯烴樹脂。
例如，可列舉碳數2~8之烯烴的單聚物或共聚物、碳數2~8之烯烴與其他單體的共聚物。具體來說，例如可列舉高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、線狀低密度聚乙烯樹脂等之聚乙烯、聚丙烯、聚異丁烯、聚(1-丁烯)、聚4-甲基戊烯、聚乙烯基環己烷、聚苯乙烯、聚(對甲基苯乙烯)、聚(α-甲基苯乙烯)、乙烯/丙烯嵌段共聚物、乙烯/丙烯無規共聚物、乙烯/丁烯-1共聚物、乙烯/4-甲基-1-戊烯共聚物、乙烯/己烯共聚物等之α-烯烴共聚物、乙烯/醋酸乙烯酯共聚物、乙烯/丙烯酸共聚物、乙烯/甲基丙烯酸甲酯共聚物、乙烯/醋酸乙烯酯/甲基丙烯酸甲酯共聚物、離子聚合物樹脂等。
又，本發明之非氯系聚烯烴樹脂(A)係含有酸價為1~200mgKOH/g之改性聚烯烴樹脂、或羥基價為1 ~200mgKOH/g之改性聚烯烴樹脂。
在本發明所使用之非氯系聚烯烴樹脂(A)係如上所述，可使用各種形式，尤其較佳的是將各種官能基(例如，羧基、羥基等)導入至聚烯烴樹脂的改性聚烯烴樹脂。甚至在該等改性聚烯烴樹脂之中，由於可更提升金屬層之密接性、耐電解質性優異，所以更佳的是具有1~200mgKOH/g之酸價的改性聚烯烴樹脂(以下，記載為酸改性聚烯烴樹脂)及/或具有1~200mgKOH/g之羥基價的改性聚烯烴樹脂(以下，記載為羥基改性聚烯烴樹脂)。
所謂的酸改性聚烯烴樹脂係在分子中具有羧基或羧酸酐基的聚烯烴樹脂，以不飽和羧酸或其衍生物將聚烯烴予以改性來合成而得。作為此改性方法，可使用接枝改性或共聚化。
酸改性聚烯烴樹脂係將至少1個可聚合之乙烯性不飽和羧酸或其衍生物針對改性前之聚烯烴樹脂予以接枝改性或共聚化後而得之接枝改性聚烯烴。改性前之聚烯烴樹脂係可列舉如上所述聚烯烴樹脂，其中，較佳的是丙烯之單聚物、丙烯與α-烯烴之共聚物、乙烯之單聚物及乙烯與α-烯烴之共聚物等。該等係可單獨使用1種或組合2種以上來使用。
作為針對改性前之聚烯烴樹脂予以接枝改性或共聚化之乙烯性不飽合羧酸或其衍生物，例如可列舉有丙烯酸、甲基丙烯酸、馬來酸、衣康酸、檸康酸、中康酸、馬來酸酐、4-甲基環己-4-烯-1,2-二羧酸酐、雙環[2.2.2]辛-5-烯-2,3-二羧酸酐、1,2,3,4,8,9,10-八氫萘-2,3- 二羧酸酐、2-辛-1,3-二酮螺[4.4]壬-7-烯、雙環[2.2.1]庚-5-烯-2,3-二羧酸酐、馬來富馬酸(maleopimaric acid)、四氫酞酸酐、甲基-雙環[2.2.1]庚-5-烯-2,3-二羧酸酐、甲基-降莰烯-5-烯-2,3-二羧酸酐、降莰-5-烯-2,3-二羧酸酐等。較佳的是可使用馬來酸酐。該等係可單獨或併用2種以上來使用。
為了使由乙烯性不飽和羧酸或其衍生物所選出之接枝單體接枝至改性前之聚烯烴樹脂上，可使用各種方法。例如，可列舉有：將聚烯烴樹脂予以熔融，於其中添加接枝單體，使進行接枝反應的方法；將聚烯烴樹脂溶解於溶媒中作成溶液，於其中添加接枝單體，使進行接枝反應的方法；將溶解於有機溶劑中之聚烯烴樹脂與上述不飽和羧酸等予以混合，在該聚烯烴樹脂之軟化溫度或熔點以上的溫度下進行加熱，以熔融狀態予以同時進行自由基聚合與去氫反應的方法等。在任一情形中，為了使該接枝單體可有效率地進行接枝共聚，較佳的是在自由基起始劑的存在下實施接枝反應。接枝反應係通常於60~350℃的條件下進行。自由基起始劑之使用比例係相對於改性前之聚烯烴樹脂100重量份而通常為0.001~1重量份的範圍。
本發明之接著劑係可使用自由基起始劑，較佳起始劑係可舉出有咪唑系自由基起始劑，但並未限定於該等。
例如，可列舉出：CUREZOL(咪唑系起始劑)、三苯基膦、1,8-重氮雙環(5.4.0)月桂烯-7(DBU)-苯酚鹽類、 DBU-辛酸鹽類等。
作為該等酸改性聚烯烴樹脂，例如可列舉有馬來酸酐改性聚丙烯、乙烯-(甲基)丙烯酸共聚物、乙烯-丙烯酸酯-馬來酸酐三元共聚物、或乙烯-甲基丙烯酸酯-馬來酸酐三元共聚物等。具體來說，已有市售品如下：三菱化學(股)製「MODIC」、三井化學(股)製「ADMER」、「UNISTOLE」、東洋紡(股)製「TOYOTAC」、三洋化成(股)製「YOUMEX」、日本聚乙烯(股)製「REXPEARL EAA」、「REXPEARL ET」、Dow Chemical(股)製「PRIMACOR」、Du Pnot-Mitsui Polychemicals(股)製「NUCREL」、ARKEMA製「BONDINE」。
羥基改性聚烯烴樹脂係在分子中具有羥基之聚烯烴樹脂，係以後述之含羥基(甲基)丙烯酸酯或含羥基乙烯基醚將聚烯烴予以接枝改性或共聚化而合成。改性前之聚烯烴樹脂或改性方法係與酸改性聚烯烴樹脂的情形相同。
作為該含羥基(甲基)丙烯酸酯，係可列舉出：(甲基)丙烯酸羥乙酯；(甲基)丙烯酸羥丙酯、(甲基)丙烯酸甘油酯；內酯改性(甲基)丙烯酸羥乙酯、(甲基)丙烯酸聚乙二醇、(甲基)丙烯酸聚丙二醇等，作為該含羥基乙烯基醚，係可列舉出：2-羥乙基乙烯基醚、二乙二醇單乙烯基醚、4-羥丁基乙烯基醚等。
本發明之接著劑係可使用自由基起始劑，較佳起始劑係可舉出有咪唑系自由基起始劑，但並未限定於該等。
例如，可列舉出：CUREZOL(咪唑系起始劑)、三苯基膦、1,8-重氮雙環(5.4.0)月桂烯-7(DBU)-苯酚鹽類、DBU-辛酸鹽類等。
(環氧化合物(B))
作為本發明之環氧化合物(B)，例如可列舉出乙二醇、丙二醇、己二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙烷、季戊四醇、丙三醇、二丙三醇、山梨糖醇、螺二醇或氫化雙酚A等之多元醇二縮水甘油醚型環氧樹脂。
此外，還可以列舉出：雙酚A、雙酚F、雙酚S、雙酚AD等二縮水甘油醚型環氧樹脂或苯酚酚醛清漆樹脂或甲苯酚酚醛清漆樹脂之縮水甘油醚的酚醛清漆型環氧樹脂等芳香族環氧樹脂；芳香族系多羥基化合物之環氧乙烷或環氧丙烷加成物等多元醇類之二縮水甘油醚型環氧樹脂。
再者，還可以列舉出：聚乙二醇、聚丙二醇或聚丁二醇等多元醚多元醇之聚縮水甘油醚型環氧樹脂；雙(3,4-環氧環己基甲基)己二酸酯、3,4-環氧環己基甲基-3',4'-環氧環己基羧酸酯等環狀脂肪族型聚環氧樹脂。
再者，還可以列舉出：丙烷三羧酸、丁烷四羧酸、己二酸、酞酸、對酞酸或1,2,4-苯三甲酸(triuncllitic acid)等聚羧酸之聚縮水甘油酯型環氧樹脂；丁二烯、己二烯、辛二烯、十二碳二烯、環辛二烯、α-蒎烯或乙烯基環己烯等烴系二烯之雙環氧樹脂。
再者，還可以列舉出：聚丁二烯或聚異戊二烯等二烯聚合物之環氧樹脂；或四縮水甘油胺二苯基甲 烷、四縮水甘油雙胺甲基環己烷、二縮水胺油苯胺或四縮水甘油甲基伸茬基二胺等縮水甘油胺型環氧樹脂、或三或尿囊素(hydantoin)之類的含有各種雜環之環氧樹脂等。
其中，當使用雙酚A型環氧樹脂等芳香族環氧樹脂，因為密接性及耐蝕性良好而較佳。
作為具體例，雙酚A型環氧樹脂係可列舉出：DIC(股)製「EPICLON 850、860、1050、1055、2055」、三菱化學(股)製「jER 828、834、1001、1002、1004、1007」等。
又，亦可為如下環氧樹脂：以在1分子中具有2個以上環氧基且在1分子中具有1個以上羥基、重量平均分子量為3000以下之環氧化合物為必要成分者。
該環氧化合物(B)係相對於該聚烯烴樹脂(A)100質量份而以0.01~30質量份的比例來配合較佳。
當少於0.01質量份時，會因為對於基材的接著力降低而不佳。
又，當多於30質量份時，會因為塗膜之凝聚力降低而不佳。
本發明之層合用接著劑係具有如下特徵：進一步含有以環狀烷烴化合物為必要成分且包括酯系溶劑或醇系溶劑的有機溶劑(C)。
本發明所使用之環狀烷烴化合物係例如可舉出有甲基環己烷等。
酯系溶劑係只要是用以發揮本發明之功效的具有酯 基之有機溶劑的話，則沒有特別限制，例如可列舉出醋酸乙酯、醋酸丁酯等。
醇系溶劑係只要是用以發揮本發明之功效的具有醇基之有機溶劑的話，則沒有特別限制，較佳為碳數1~4之脂肪族醇。
本發明之層合用接著劑係具有如下特徵：含有以環狀烷烴化合物為必要成分且包括酯系溶劑或醇系溶劑的有機溶劑(C)，以環狀烷烴化合物之質量份與其以外之溶劑之質量份的比率為1/1~20/1之範圍所構成者。
藉由該構成之含有有機溶劑(C)，則溶液安定性可提升，塗敷性變得良好，藉此，可謀求本發明之課題之耐電解質性的改良。
關於此功效，係可經由後述實施例、比較例而清楚得知。
又，藉由含有該等有機溶劑，則變得可進行乾式層合，即便是在低於習知之溫度下的熟成，也可大幅度提升原所不足之對於金屬層的密接力，可改善接著性能。
於在本構成之範圍外時，接著劑會凝膠化而無法解決本發明之課題。
(其他添加劑)
在本發明中，作為其他添加劑，可使用公知慣用之熱塑性彈性體、黏著賦予劑、觸媒、磷酸化合物、三聚氰胺樹脂、矽烷偶合劑或反應性彈性體。該等添加劑之含量係可在不損及本發明之接著劑功能的範圍內予以適 當調整而使用。
(積層體)
本發明之積層體係將本發明之層合用接著劑組成物與鋁箔等金屬層、聚乙烯、聚丙烯等聚烯烴片材、聚對苯二甲酸乙二酯等聚酯等的1種或數種的塑膠層予以貼合而獲得者。
然後，本發明之層合用接著劑組成物係例如能夠以任意比例使於酯系溶劑、酮系溶劑、芳香族烴、脂肪族烴、脂環族烴等之適當溶劑或分散劑中進行溶解/分散，採用輥塗法、凹版印刷塗法、棒塗法等周知塗佈方法而在金屬箔上進行塗佈、乾燥，藉以形成接著層。
本發明之層合用接著劑組成物之乾燥塗佈重量係以0.5~30.0g/m2的範圍內為佳。當小於0.5g/m2時，會在連續均勻塗佈性方面產生難題，另一方面，當超過30.0g/m2時，塗佈後之溶劑脫離性亦會降低，在作業性明顯降低的狀態下，產生殘留溶劑的問題。
在將本發明之層合用接著劑組成物塗敷於該金屬箔之其一面上之後，可透過乾式層合法(乾式積層法)重疊塑膠層進行貼合，依此獲得本發明之積層體。較佳的是：層合輥溫度為室溫~120℃左右，壓力為3~100kg/cm2。
又，本發明之積層體係以在製作後進行熟成為佳。熟成條件係在室溫~100℃下，12~240小時之間，此期間內會產生接著強度。
(二次電池)
本發明之積層體係可當作一次或二次電池之電解液密封薄膜或電極部保護薄膜來使用，此時，係可使塑膠層側與極性有機溶媒及/或鹽類等進行接觸而使用。尤其是藉由以使包含極性有機溶媒及鹽類之非水電解質進行接觸的狀態來使用，而特別是可當作為非水電解質電池、固體電池等之二次電池電解液密封薄膜或二次電池電極部保護薄膜來適當使用。此時，能夠以塑膠層相對向的方式進行摺疊並予熱封，藉以當作為電池用密封袋來使用。本發明中所使用之接著劑係因熱封性優異，而可防止非水電解質之洩漏，能當作電池而長期使用。
作為該極性有機溶媒，可列舉出非質子性之極性溶媒，例如烷基碳酸酯、酯、酮等。具體來說，可列舉出碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、碳酸二甲酯、碳酸乙基甲酯、碳酸二乙酯、γ-丁內酯、1,2-二甲氧基乙烷、四氫呋喃、2-甲基四氫呋喃、1,3-二、4-甲基-1,3-二、甲酸甲酯、4-甲基-1,3-二側氧甲基甲酸酯、醋酸甲酯、丙酸甲酯等。作為鹽類，可列舉有鋰鹽、鈉鹽、鉀鹽等鹼金屬鹽類。電池上所一般使用的是LiPF6、LiBF4、Li-醯亞胺等鋰鹽。
非水電解質係該鹼金屬鹽類在環狀碳酸酯、鏈狀碳酸酯、該等之混合物等之非質子性極性有機溶媒中溶解有0.5~3mmol者。
本發明之積層體係即便是在以與該極性溶媒及/或鹽類，尤其是該等之混合物之非水電解質接觸的狀態而使用，仍難以產生金屬層、接著層、塑膠層之層間剝離 ，可經過長期間來使用。
本發明之電池係具有包括該積層體之電池電解液密封薄膜或電池電極部保護薄膜的電池。本發明之電池係上述薄膜不會產生層間剝離，而且可防止非水電解質之洩漏，故而可當作為電池而長期間安定來使用。
如上所述，本發明之積層體係金屬層與塑膠層之接著力優異，同時對於極性有機溶媒或鹽類的耐久性優異，即便與非水電解質等接觸也不會產生層間剝離。因此，將此類積層體當作為電池電解液密封薄膜或二次電池電極部保護薄膜來使用的電池、及當作為二次電池電解液密封薄膜或二次電池電極部保護薄膜來使用的二次電池係可長期間安定使用。於此，二次電池係可舉出可撓性封裝型者，但並未限定於此。
[實施例]
以下，透過實施例來具體說明本發明。表中所載「份」係表示質量份。
(實施例1)
添加50份之改性聚醯烴樹脂GMP7550E(羅德化學公司製)、50份之AUROREN 350S、0.05份之CUREZOL 2E4MZ、6.0份之DENACOL EX-850L、320份之甲基環己烷、40份之醋酸乙酯、40份之異丙醇(IPA)並予以仔細攪拌，利用棒塗機在鋁箔上塗佈5gm2(乾的)，於80℃ -1分鐘乾燥之後，在100℃下與CPP薄膜貼合，製作塗敷物。
其後，在使進行60℃ -5天熟成之後，測量初期接著強度。
將其他接著劑如表1所示般進行配合，與實施例1同樣地進行操作，製作接著劑。接著，藉由與積層體1同樣的製作方法來製作各積層體。
針對在各例中所獲得之積層體，評估接著性能及耐電解質性，將其結果示於表1。另外，各性能試驗條件係如下所述。
(初期接著強度的測量)
在A&T製TENSILON試驗中，將試料裁成15mm寬度，測量180°剝離強度。
(耐電解液性)
使積層體以80℃ -7天的條件浸漬在「碳酸伸乙酯：碳酸乙基甲基酯：碳酸二甲酯=1：1：1(wt%)+LiPF6：1mol+碳酸伸乙烯酯：1wt%」中，自浸漬前後之接著強度的保持率來實施如下的評估。
○：80%以上、△：80~70%、×：70%以下
比較例係如表2中所示來進行配合，與實施例同樣地進行操作，製作積層體。此外，使用該積層體，評估接著強度、耐電解液性。
將結果示於表2。
‧GMP7550E(羅德化學公司製)馬來酸改性聚烯烴樹脂
不揮發分100%
‧AUROREN 350S(日本製紙公司製)馬來酸酐改性聚醯烴樹脂
不揮發分100%
‧CUREZOL 2E4MZ(四國化成工業股份有限公司製)咪唑 不揮發分100%
‧DENACOL EX-850L(NAGASECHEMTEX股份有限公司製)脂肪族環氧樹脂
環氧當量145 不揮發分100%
‧EPICLON 860(DIC股份有限公司製)雙酚A型環氧樹脂 環氧當量240 不揮發分100%
‧GMP7550E(羅德化學公司製)馬來酸改性聚烯烴樹脂
不揮發分100%
‧AUROREN 350S(日本製紙公司製)馬來酸酐改性聚醯烴樹脂
不揮發分100%
‧CUREZOL 2E4MZ(四國化成工業股份有限公司製)咪唑 不揮發分100%
‧DENACOL EX-850L(NAGASECHEMTEX股份有限公司製)脂肪族環氧樹脂
環氧當量145 不揮發分100%
‧EPICLON 860(DIC股份有限公司製)雙酚A型環氧樹脂
環氧當量240 不揮發分100%
由上述結果可知，含有本發明之構成之有機溶劑的層合用接著劑係可解決本案發明之課題。
[產業上之可利用性]
本發明之層合用接著劑係因為金屬層與塑膠層之接著性優異，滿足防濕性、耐熱性、絕緣性、耐久性等，甚至即便是於低溫熟成也可兼備耐電解質性，且隨時間不會產生層間剝離，而可當作為二次電池用之積層體來使用。

Claims (8)

  1. 一種層合用接著劑，其係含有非氯系聚烯烴樹脂(A)、環氧化合物(B)、及以環狀烷烴化合物為必要成分且包括酯系溶劑或醇系溶媒之有機溶劑(C)，其中，有機溶劑(C)係以環狀烷烴化合物之質量份與其以外之溶劑之質量份的比率為1/1~20/1之範圍所構成。
  2. 如請求項1之層合用接著劑，其中環狀烷烴化合物為甲基環己烷，酯系溶劑為乙酸乙酯，醇系溶媒為碳數1~4之脂肪族醇。
  3. 如請求項1或2之層合用接著劑，其中該非氯系聚烯烴樹脂(A)係含有酸價為1~200mgKOH/g之改性聚烯烴樹脂或羥基價為1~200mgKOH/g之改性聚烯烴樹脂。
  4. 如請求項1或2之層合用接著劑，其中環氧化合物(B)係以一分子中具有2個以上環氧基且一分子中具有1個以上羥基，且重量平均分子量為3000以下之環氧化合物為必要成分。
  5. 如請求項1或2之層合用接著劑，其中相對於該非氯系聚烯烴樹脂(A)100質量份，環氧化合物(B)係以0.01~30質量份的比例來摻合。
  6. 如請求項1或2之層合用接著劑，其可進一步含有熱塑性彈性體、黏著賦予劑、觸媒、磷酸化合物、三聚氰胺樹脂、矽烷偶合劑或反應性彈性體。
  7. 一種積層體，其係將如請求項1至6項中任一項之層合用接著劑使用在金屬層與聚烯烴樹脂層間而成。
  8. 一種二次電池，其係將如請求項7之積層體當作電解液密封薄膜或電極部保護薄膜來使用。
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WO2016042837A1 (ja) 2016-03-24
EP3196266A4 (en) 2018-05-02
CN105658753B (zh) 2017-06-13
KR20160047468A (ko) 2016-05-02
JPWO2016042837A1 (ja) 2017-04-27
KR20180010328A (ko) 2018-01-30
KR101925264B1 (ko) 2018-12-04
US20170088753A1 (en) 2017-03-30

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