TW201737525A - 包裝材、外殼及蓄電裝置 - Google Patents
包裝材、外殼及蓄電裝置 Download PDFInfo
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- TW201737525A TW201737525A TW105127723A TW105127723A TW201737525A TW 201737525 A TW201737525 A TW 201737525A TW 105127723 A TW105127723 A TW 105127723A TW 105127723 A TW105127723 A TW 105127723A TW 201737525 A TW201737525 A TW 201737525A
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- Prior art keywords
- layer
- heat
- packaging material
- adhesive
- resin layer
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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Abstract
本發明係提供一種包裝材,其構成係包含外側層之耐熱性樹脂層2、內側層之熱熔著性樹脂層3、及於該兩層間配置之金屬箔層4;其中,耐熱性樹脂層2,係由熱水收縮率1.5%~12%之耐熱性樹脂薄膜所成,耐熱性樹脂層2與金屬箔層4係介由外側接著劑層5而接著,該外側接著劑層5,係由聚胺甲酸酯接著劑所形成,且該聚胺甲酸酯接著劑係含有:多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物。藉由此構成,可成為即使進行成形深度深的成形,亦可充分抑止層間剝離且不產生針孔等,確保優良成形性之包裝材。
Description
本發明,例如,係關於一種可合適地作為二次電池(例如,鋰離子蓄電池等)等之蓄電裝置之包裝材(外裝材)、外殼使用;抑或可合適作為食品、醫藥品之包裝材使用,且進一步關於此等包裝材或/及外殼所外裝而成之蓄電裝置。
此外,本說明書及申請專利範圍中,「鋁」之詞彙,係意指包含鋁及其合金的意思。
鋰離子蓄電池,目前已廣泛作為例如筆記型電腦、攝影機、手機、電動汽車等之電源使用。此鋰離子蓄電池,係使用以外殼包圍電池本體部(包含正極、負極及電解質之本體部)周圍之構成者。此外殼用材料(外裝材),習知係耐熱性樹脂薄膜構成之外層、鋁箔層、熱可塑性樹脂薄膜構成之內層依序接著一體化所成之構成者。
例如,已知的一種包裝材,其係具備樹脂薄膜構成之內層、第1接著劑層、金屬層、第2接著劑層、及樹脂薄膜構成之外層;前述第1接著劑層及第2接著劑層之至少一者,其側鏈係具有活性氫基之樹脂、多官能異氰酸酯類、及多官能胺化合物作為必要成分之接著劑組成物所成
之包裝材(參照專利文獻1)。
此外,習知的一種電池外殼用包材,係使用至少鋁箔之單面上,層壓厚度9~50μm之聚醯胺薄膜或聚酯薄膜,且於最外側層壓至少厚度9~50μm之聚丙烯、馬來酸變性聚丙烯、乙烯-丙烯酸酯共聚合物或離聚物樹脂之薄膜,聚醯胺薄膜或聚酯薄膜之拉伸試驗中4方向(0°、45°、90°及135°)至斷裂之拉伸強度為150N/mm2以上,且4方向之延伸為80%以上之聚醯胺薄膜或聚酯薄膜(參照專利文獻2)。
專利文獻1:日本特開2008-287971號公報
專利文獻2:日本特開2000-123800號公報
然而,前述專利文獻1、2所記載之技術,無法兼顧作為包裝材之充分的耐熱性與優良成形性兩者。
此外,專利文獻1所記載之包裝材,於進行成形深度深的成形時,金屬箔層及外側樹脂層之間容易發生脫層(剝離),在高溫潮濕的嚴苛環境下使用時,金屬箔層及外側樹脂層之間容易發生層間剝離。
此外,專利文獻2所記載之包裝材,進行成形深度深的成形
時,應力會集中於金屬箔之局部,有容易產生針孔或裂縫之問題。
本發明鑑於相關技術背景,目的在於提供一種具備耐熱性,且進行成形深度深的成形亦不會產生針孔或裂縫而可確保優良成形性,且進行成形深度深的成形或高溫潮濕的嚴苛環境下使用亦可充分抑制層間剝離(剝離)之包裝材及外殼。此外,另一目的在於提供此種包裝材或/及外殼所外裝而成之蓄電裝置。
為了達成前述目的,本發明提供以下技術手段。
〔1〕一種包裝材,其特徵為其係包含外側層之耐熱性樹脂層、內側層之熱熔著性樹脂層、及配置於此兩層間之金屬箔層之包裝材;其中,前述耐熱性樹脂層,係由熱水收縮率為1.5%~12%之耐熱性樹脂薄膜所成,前述耐熱性樹脂層與前述金屬箔層係介由外側接著劑層而接著,前述外側接著劑層,係由聚胺甲酸酯接著劑所形成,且該聚胺甲酸酯接著劑係含有:多元醇、多官能異氰酸酯化合物、及1分子中具有能夠與複數個異氰酸酯基反應之官能基之脂肪族化合物。
〔2〕如前項1所記載之包裝材,其中,前述多元醇,係聚酯多元醇。
〔3〕如前項2所記載之包裝材,其中,前述聚酯多元醇,係包含二羧酸成分,前述二羧酸成分,係含有芳香族二羧酸,且前述二羧
酸成分中前述芳香族二羧酸之含有率為40莫耳%~80莫耳%。
〔4〕如前項1~3中任1項所記載之包裝材,其中,前述脂肪族化合物,係多價醇。
〔5〕如前項1~4中任1項所記載之包裝材,其中,前述外側接著劑層,係含有選自胺甲酸酯鍵、酯鍵、脲鍵、脲甲酸酯鍵、雙縮脲鍵及醯胺鍵所成群中之至少1種鍵結。
〔6〕如前項1~5中任1項所記載之包裝材,其中,前述耐熱性樹脂層與前述外側接著劑層之間係配置有易接著層。
〔7〕如前項6所記載之包裝材,其中,前述易接著層,係含有選自環氧樹脂、胺甲酸酯樹脂、丙烯酸酯樹脂、甲基丙烯酸酯樹脂及聚乙烯亞胺樹脂所成群中之1種或2種以上樹脂。
〔8〕如前項1~7中任1項所記載之包裝材,其中,前述胺甲酸酯接著劑之硬化膜之楊氏模量係90MPa~400MPa。
〔9〕一種由前項1~8中任1項所記載之包裝材之成形體所構成之外殼。
〔10〕一種外殼之製造方法,其特徵係,將前項1~8中任1項所記載之包裝材深引伸成形或鼓脹成形。
〔11〕一種蓄電裝置,其特徵係具備蓄電裝置本體部、前項1~8中任1項所記載之包裝材及/或前項9所記載之外殼所構成之外裝部材;前述蓄電裝置本體部以前述外裝部材所外裝而成。
〔12〕一種包裝材之製造方法,其特徵係包含積層物之準
備步驟:前述積層物包含外側層之耐熱性樹脂層、內側層之熱熔著性樹脂層、於該兩層間配置之金屬箔層;其中,前述耐熱性樹脂層係由熱水收縮率1.5%~12%之耐熱性樹脂薄膜所成,前述熱熔著性樹脂層與前述金屬箔層係介由硬化型內側接著劑層而接著,前述耐熱性樹脂層與前述金屬箔層係介由硬化型外側接著劑層而接著,且前述硬化型外側接著劑層係多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物;及老化處理步驟:藉由將前述積層物在37℃~55℃範圍之溫度下進行加熱老化處理,使前述硬化型內側接著劑及前述硬化型外側接著劑硬化。
〔13〕如前項12所記載之包裝材之製造方法,其中,前述硬化型內側接著劑為熱硬化型丙烯酸接著劑。
〔1〕之發明,因外側層之耐熱性樹脂層係由熱水收縮率1.5%~12%之耐熱性樹脂薄膜所構成,故可抑制由於深引伸成形、鼓脹成形等之冷間(常溫)成形之應力集中,藉此,進行成形深度深的成形不會產生針孔或裂縫而可確保優良的成形性。
此外,因耐熱性樹脂層及金屬箔層介由聚胺甲酸酯接著劑而接著之構成,且該聚胺甲酸酯接著劑係含有:多元醇、多官能異氰酸酯化合物、及1分子中具有複數個含有能夠與異氰酸酯基反應之官能基之脂肪族化合物,可提升包裝材之耐熱性。
更進一步,由於其係i)前述耐熱性樹脂層(外側層)係由
熱水收縮率1.5%~12%之耐熱性樹脂薄膜所形成之構成,且ii)耐熱性樹脂層及金屬箔層介由聚胺甲酸酯接著劑而接著之構成,且該聚胺甲酸酯接著劑係含有:多元醇、多官能異氰酸酯化合物、及1分子中具有複數個含有能夠與異氰酸酯基反應之官能基之脂肪族化合物,故進行成形深度深的成形或在高溫潮濕的嚴苛環境下使用亦可充分抑制層間剝離(剝離)。
此外,因外側接著劑使用含有多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物之聚胺甲酸酯接著劑,比傳統接著劑低的溫度亦能促進硬化反應。
傳統上,一般比起熱熔著性樹脂層側之接著劑(內側接著劑)之最合適老化溫度(促進硬化反應之溫度),耐熱性樹脂層側之接著劑(外側接著劑)之最合適老化溫度(促進硬化反應之溫度)較高之情形較多,如此之情形,內側接著劑之硬化反應之第1老化處理,及外側接著劑之硬化反應之第2老化處理必須分成2次進行,因此生產效率不佳,而本案發明,因外側接著劑使用含有多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物之聚胺甲酸酯接著劑,在比傳統接著劑低的溫度進行硬化,1次的老化處理內,內側接著劑及外側接著劑能同時一併老化處理,藉此有縮短交貨時間(從投入資材至產品完成之所需時間)之優點。此外,〔12〕之發明,係製造此種1次的老化處理內,硬化型內側接著劑及硬化型外側接著劑能同時一併老化處理使包裝材硬化之方法。
〔2〕之發明,可進一步縮短交貨時間而可減低成本。
〔3〕之發明,聚酯多元醇包含二羧酸成分,該二羧酸成分
中之芳香族二羧酸之含有率為40莫耳%~80莫耳%之構成,而藉由芳香族二羧酸之含有率為40莫耳%~80莫耳%,因此主劑(聚酯多元醇)之骨架變硬、耐熱性上升、外側接著劑層之接著強度增大、成形性上升。因此,進行成形深度深的成形時,可充分防止外側層及金屬箔層間的層間剝離(剝離)。
〔4〕之發明,由於前述脂肪族化合物使用多價醇,故進行成形深度深的成形時,可進一步充分防止外側層及金屬箔層間的層間剝離。
〔5〕之發明,由於外側接著劑層選自胺甲酸酯鍵、酯鍵、脲鍵、脲甲酸酯鍵、雙縮脲鍵及醯胺鍵所成群中之至少1種鍵結,可增大外側接著劑層之接著強度、亦可提升成形性。因此,進行成形深度深的成形時,能更充分防止外側層及金屬箔層間的層間剝離。
〔6〕之發明,因耐熱性樹脂層及外側接著劑層之間配置易接著層,即使在高溫潮濕等嚴苛的環境下使用,可充分防止外側層及金屬箔層間的層間剝離。
〔7〕之發明,由於易接著層係含有前述特定樹脂之構成,即使在高溫潮濕等嚴苛的環境下使用,可充分防止外側層及金屬箔層間的層間剝離。
〔8〕之發明,因採用胺甲酸酯接著劑之硬化膜之楊氏模量為90MPa~400MPa之構成,可更提升成形性,提升外側接著劑層之耐久性。
〔9〕之發明,提供具備耐熱性,進行成形深度深的成形亦不產生針孔或裂縫而能確保優良成形性,且進行成形深度深的成形或在高
溫潮濕等嚴苛的環境下使用亦能充分防止層間剝離之外殼。
〔10〕之發明,可製造具備耐熱性,進行成形深度深的成形亦不產生針孔或裂縫而能確保優良成形性,且進行成形深度深的成形或在高溫潮濕等嚴苛的環境下使用亦能充分防止層間剝離之外殼。
〔11〕之發明,可提供具備耐熱性,不存在針孔或裂縫而能確保優良成形性,且進行成形深度深的成形或在高溫潮濕等嚴苛的環境下使用亦能充分防止層間剝離之外裝部材所外裝而成之蓄電裝置。
〔12〕之發明(製造方法),可製造具備耐熱性,進行成形深度深的成形亦不產生針孔或裂縫而能確保優良成形性,且進行成形深度深的成形或在高溫潮濕等嚴苛的環境下使用亦能充分防止層間剝離之包裝材。
更進一步,外側接著劑層使用含有多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基脂肪族化合物之硬化型外側接著劑,該硬化型外側接著劑,可在比以往低的37℃~55℃之溫度範圍下促進硬化反應,藉此,可在1次的老化處理內,硬化型內側接著劑及硬化型外側接著劑兩者同時一併老化使兩者之接著劑同時硬化,因此具有顯著提升生產效率之優點。
〔13〕之發明,因硬化型內側接著劑使用熱硬化型丙烯酸接著劑,硬化型內側接著劑及硬化型外側接著劑之間各自促進硬化反應之溫度範圍的一致性高,所以可縮短老化處理時間,更提升生產效率。
1‧‧‧包裝材
2‧‧‧耐熱性樹脂層(外側層)
3‧‧‧熱熔著性樹脂層(內側層)
4‧‧‧金屬箔層
5‧‧‧第1接著劑層(外側接著劑層)
6‧‧‧第2接著劑層(內側接著劑層)
8‧‧‧易接著層
10‧‧‧外殼(成形外殼)
15‧‧‧外裝部材
30‧‧‧蓄電裝置
31‧‧‧蓄電裝置本體部
【圖1】本發明之包裝材之一實施型態之斷面圖;【圖2】本發明之包裝材之其他實施型態之斷面圖;【圖3】本發明之蓄電裝置之一實施型態之斷面圖;【圖4】構成圖3之蓄電裝置之包裝材(平面狀者)、蓄電裝置本體部及外殼(成形為立體形狀之成形體)熱密封前之分離狀態之斜視圖。
以圖1表示本發明之包裝材1之一實施型態。此包裝材1,係用於鋰離子蓄電池等之電池用包裝材。前述包裝材1,亦可在未施予成形之狀態下直接作為包裝材1使用(參照圖4),例如,亦可使用進行深引伸成形、鼓脹成形等成形之外殼10(參照圖4)。
前述包裝材1,係金屬箔層4之一側之面(上面)介由外側接著劑層(第1接著劑層)5而與耐熱性樹脂層(外側層)2積層一體化,且前述金屬箔層4之另一側之面(下面)介由內側接著劑層(第2接著劑層)6而與熱熔著性樹脂層(內側層)3積層一體化之構成(參照圖1)。
以圖2表示本發明之包裝材1之其他實施型態。此包裝材1,係金屬箔層4之一側之面(上面)介由外側接著劑層(第1接著劑層)5而與耐熱性樹脂層(外側層)2積層一體化,且前述金屬箔層4之另一側之面(下面)介由內側接著劑層(第2接著劑層)6而與熱熔著性樹脂層(內側層)3積層一體化之構成,並進一步於前述耐熱性樹脂層(外側層)2之下面積層易接著層8,於該易接著層8之下面積層前述外側接著
劑層(第1接著劑層)5。亦即,形成耐熱性樹脂層(外側層)2/易接著層8/外側接著劑層5/金屬箔層4/內側接著劑層6/熱熔著性樹脂層(內側層)3之積層構造(參照圖2)。本實施型態,係藉由凹版塗佈法於前述耐熱性樹脂層2之下面積層易接著層8。
本發明中,前述外側層2,係以耐熱性樹脂層形成。構成前述耐熱性樹脂層2之耐熱性樹脂,係使用不會因熱密封包裝材1時之熱密封溫度而溶融之耐熱性樹脂。前述耐熱性樹脂,使用具有比構成熱熔著樹脂層3之熱熔著性樹脂之熔點高10℃以上熔點之耐熱性樹脂為佳,使用具有比熱熔著性樹脂之熔點高20℃以上熔點之耐熱性樹脂為特佳。
前述耐熱性樹脂層(外側層)2,係主要發揮確保包裝材1之良好的成形性之作用的部材,亦即主要發揮防止因成形時之鋁箔之縮頸而斷裂之作用者。
本發明中,前述耐熱性樹脂層2,必須係由熱水收縮率1.5%~12%之耐熱性樹脂薄膜所構成。熱水收縮率未達1.5%會發生成形時容易產生破損或裂縫之問題。另一方面,熱水收縮率超過12%時,則外側層2及金屬箔層4之間容易發生層間剝離(剝離)。其中,前述耐熱性樹脂薄膜,使用熱水收縮率1.8~11%之耐熱性樹脂薄膜為佳。更進一步,使用熱水收縮率1.8%~6%之耐熱性樹脂薄膜更佳。前述耐熱性樹脂薄膜使用耐熱性樹脂延伸薄膜為佳。
又,前述「熱水收縮率」,係將耐熱性樹脂延伸薄膜2之試驗片(10cm×10cm)浸漬95℃之熱水中30分,試驗片之浸漬前後之延伸方向之尺寸變化率,以下式求得。
熱水收縮率(%)={(X-Y)/X}×100
X:浸漬處理前之延伸方向之尺寸
Y:浸漬處理後之延伸方向之尺寸。
又,採用2軸延伸薄膜時,其熱水收縮率為2個延伸方向之尺寸變化率之平均值。
前述耐熱性樹脂延伸薄膜之熱水收縮率,例如,可藉由調整延伸加工時之熱固定溫度來控制。
前述耐熱性樹脂層(外側層)2,並無特別限定,可列舉例如,延伸尼龍薄膜等之延伸聚醯胺薄膜、延伸聚酯薄膜等。其中,特佳係前述耐熱性樹脂層2,使用二軸延伸尼龍薄膜等之二軸延伸聚醯胺薄膜、二軸延伸聚對苯二甲酸丁二酯(PBT)薄膜、二軸延伸聚對苯二甲酸乙二酯(PET)薄膜或二軸延伸聚萘二甲酸乙二酯(PEN)薄膜且熱水收縮率皆為1.5%~12%者。此外,前述耐熱性樹脂層2,使用藉由同時2軸延伸法延伸之耐熱性樹脂2軸延伸薄膜為佳。前述尼龍,可列舉例如,6尼龍、6,6尼龍、MXD尼龍等。此外,前述耐熱性樹脂層2,亦可形成為單層(單一之延伸薄膜),或例如亦可形成為延伸聚酯薄膜/延伸聚醯胺薄膜所構成之複層(延伸PET薄膜/延伸尼龍薄膜所構成之複層等)。
前述耐熱性樹脂層2之厚度係在12μm~50μm為佳。設定在前述合適的下限值以上可確保包裝材充分的強度,且設定在前述合適的上限值以下可減小引伸成形或鼓脹成形時之應力,從而可提升成形性。
前述耐熱性樹脂層2之內面(金屬箔層4側之面),係積層易接著層8為佳。於前述耐熱性樹脂層2之內面(金屬箔層4側之面),藉由塗佈黏著性、接著性優良之極性樹脂等而積層易接著劑層8,可提升與前述外側接著劑層5之密著性、接著性,藉此可提升耐熱性樹脂層2與金屬箔層4之密著性、接著性。此外,前述耐熱性樹脂層2之內面(積層易接著層8之面),積層易接著層8前預先進行電暈處理提高潤濕性為佳。
前述易接著層8之形成方法,並無特別限定,例如,可藉由於耐熱性樹脂薄膜2之表面,塗佈環氧樹脂、胺甲酸酯樹脂、丙烯酸酯樹脂、甲基丙烯酸酯樹脂及聚乙烯亞胺樹脂所成群中之1種或2種以上樹脂之水性乳膠(水系乳膠)後乾燥,從而形成易接著層8。前述塗佈方法,並無特別限定,可列舉例如,噴霧塗佈法、凹版塗佈法、逆輥塗佈法、唇塗佈法等。
因此,易接著層8,係含有選自環氧樹脂、胺甲酸酯樹脂、丙烯酸酯樹脂、甲基丙烯酸酯樹脂及聚乙烯亞胺樹脂所成群中之1種或2種以上樹脂之構成為佳。藉由採用此種構成,可進一步提升耐熱性樹脂層2與外側接著劑層5之接著力,此包裝材進行深引伸成形、鼓脹成形等之成形時,為了密封而熱密封包裝材時,可充分防止外側層(耐熱性樹脂層)2及金屬箔層4之間發生層間剝離(剝離),且即使包裝材1在高溫潮濕等嚴苛的環境下使用時,可充分防止外側層(耐熱性樹脂層)2及金屬箔層4之間發生層間剝離(剝離)。
其中,前述易接著層8,係含有胺甲酸酯樹脂及環氧樹脂之構成,或含有(甲基)丙烯酸酯樹脂及環氧樹脂之構成為特佳。於此情形,
可更加充分抑制外側層(耐熱性樹脂層)2及金屬箔層4之間發生層間剝離(剝離)。
採用上述前者之構成時,易接著層8中胺甲酸酯樹脂/環氧樹脂之含有質量比在98/2~40/60之範圍為佳,此時可更提升耐熱性樹脂層2與外側接著劑層5之接著力。相較於前述胺甲酸酯樹脂/環氧樹脂之含有質量比(98/2),胺甲酸酯樹脂之含有比率較大時,交聯度會不足、難以充分得到耐溶劑性、接著力,故不佳。另一方面,相較於前述胺甲酸酯樹脂/環氧樹脂之含有質量比(40/60),胺甲酸酯樹脂之含有比率較小時,交聯完成所需時間過長,故不佳。其中,易接著層8中胺甲酸酯樹脂/環氧樹脂之含有質量比在90/10~50/50之範圍為更佳。
此外,採用上述後者之構成時,易接著層8中(甲基)丙烯酸酯樹脂/環氧樹脂之含有質量比在98/2~40/60之範圍為佳,此時可更提升耐熱性樹脂層2與外側接著劑層5之接著力。相較於前述(甲基)丙烯酸酯樹脂/環氧樹脂之含有質量比(98/2),(甲基)丙烯酸酯樹脂之含有比率較大時,交聯度會不足、難以充分得到耐溶劑性、接著力而不佳。另一方面,相較於(甲基)丙烯酸酯樹脂/環氧樹脂之含有質量比(40/60),(甲基)丙烯酸酯樹脂之含有比率較小時,交聯完成所需時間過長,故不佳。其中,易接著層8中(甲基)丙烯酸酯樹脂/環氧樹脂之含有質量比在90/10~50/50之範圍為更佳。
形成前述易接著層8之前述樹脂水性乳膠(樹脂-水系乳膠)中,可添加乙二醇類、乙二醇之環氧乙烷加成物等之界面活性劑,此
時樹脂水性乳膠中可得到充分的消泡效果,因此可形成表面平滑性優良的易接著層8。前述界面活性劑於前述樹脂水性乳膠中含有0.01質量%~2.0質量%為佳。
此外,形成前述易接著層8之前述樹脂水性乳膠(樹脂-水系乳膠)中,含有二氧化矽、膠體二氧化矽等之無機微粒子為佳,此時可得到防結塊效果。前述無機微粒子,相對於前述樹脂份100質量份添加0.1質量份~10質量份為佳。
前述易接著層8之形成量(乾燥後之固體分量)為0.01g/m2~0.5g/m2之範圍為佳。藉由在0.01g/m2以上,可充分接著耐熱性樹脂層2與外側接著劑層5;藉由在0.5g/m2以下,可經濟性減低成本。
前述易接著層(乾燥後)8中前述樹脂之含有率為88質量%~99.9質量%為佳。
本發明中,前述外側接著劑層(第1接著劑層)5,係含有多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物之聚胺甲酸酯接著劑所形成。
前述多元醇,並無特別限定,例如,可例舉聚酯多元醇、多價多元醇、聚醚多元醇、聚酯聚胺甲酸酯多元醇、聚醚聚胺甲酸酯多元醇等。其中,前述多元醇使用聚酯多元醇在可提升耐熱性之處為佳。
前述聚酯多元醇,例如,藉由混合醇及羧酸進行縮聚合反應而得到。亦即,前述聚酯多元醇為醇成分及羧酸成分之縮聚合體。例如,藉由混合多價醇及二羧酸於210℃進行縮聚合反應20小時,可製造前
述聚酯多元醇。前述多價醇,並無特別限定,例如,可例舉新戊二醇、乙二醇、1,6-己二醇等。前述羧酸,並無特別限定,例如,可例舉脂肪族二羧酸、芳香族二羧酸等二羧酸。前述脂肪族二羧酸,並無特別限定,例如可例舉,己二酸、丁二酸、己二酸、辛二酸、癸二酸等,前述芳香族二羧酸,並無特別限定,例如,可例舉,間苯二甲酸、對苯二甲酸、萘二羧酸、苯二甲酸酐等。
前述聚酯多元醇之前述二羧酸成分係含有前述芳香族二羧酸為佳。前述二羧酸成分中芳香族二羧酸之含有率在40莫耳%~80莫耳%為佳。藉由在40莫耳%以上,即使進行深度深的成形時,亦可更充分防止外側層2及金屬箔層4間之層間剝離(剝離),且藉由在80莫耳%以下,可充分確保外側接著劑(第1接著劑)5之密著力。其中,前述二羧酸成分中芳香族二羧酸之含有率在50莫耳%~70莫耳%為更佳。
前述多元醇的數量平均分子量,雖無特別限定,惟在8000~30000之範圍為佳,在10000~26000之範圍特佳。
前述多官能異氰酸酯化合物(硬化劑),可使用脂肪族系、脂環族系、芳香族系之各種多官能異氰酸酯化合物。前述脂肪族系多官能異氰酸酯化合物,例如,可例舉六亞甲基二異氰酸酯(HMDI)等,前述脂環族系多官能異氰酸酯化合物,例如,可例舉異佛爾酮二異氰酸酯(IPDI)等,前述芳香族系多官能異氰酸酯化合物,例如,可例舉甲苯二異氰酸酯(TDI)、二苯甲烷二異氰酸酯(MDI)等。亦可係此等多官能異氰酸酯化合物之變性體,例如,可例示為異氰脲酸酯化、碳二亞胺化、聚合化等經多量化反應之多官能異氰酸酯變性體。
前述脂肪族化合物,使用1分子中具有複數個能夠與異氰酸酯基(NCO)反應之官能基之脂肪族化合物。前述脂肪族化合物中,亦包含結合氧、氮、硫、氯等原子之化合物。此外,前述脂肪族化合物中,不含具有芳香環之化合物。此外,前述脂肪族化合物中,不含前述多元醇及前述多官能異氰酸酯化合物。前述脂肪族化合物,使用比前述多元醇之數量平均分子量更小者為佳。其中,前述脂肪族化合物之分子量,在60~9500之範圍為佳,其中在100~1000之範圍為更佳。
與前述異氰酸酯基(NCO)可反應之官能基,並無特別限定,例如可例舉,羥基、胺基、羧基等。
前述「1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物」,具體而言,並無特別限定,可列舉例如,多價醇、脂肪族二胺、二羧酸等。前述多價醇,1分子中醇性羥基具有2個以上之醇。前述多價醇,並無特別限定,例如,可例舉三羥甲基丙烷(TMP)、甲基戊二醇、二甲基二丁醇、乙二醇、丙三醇、卡必醇、己六醇等。
前述外側接著劑層5,相對前述多元醇之羥基(OH)之莫耳數,前述多官能異氰酸酯化合物之異氰酸酯基(NCO)之莫耳數之比率(當量比〔NCO〕/〔OH〕),設定在2~25之範圍為佳。其中,前述當量比〔NCO〕/〔OH〕,設定在5~20之範圍為特佳。
前述外側接著劑層(第1接著劑層)5之厚度(乾燥後之厚度),設定在1μm~6μm為佳。
構成前述外側接著劑層5之胺甲酸酯接著劑之硬化膜的楊氏模量在90MPa~400MPa之範圍之構成為佳。藉由楊氏模量在
90MPa以上,可提升外側接著劑層5之耐熱性,即使進行成形深度深的成形,可充分防止外側層2及金屬箔層4間發生層間剝離(剝離),且藉由楊氏模量在400MPa以下,可充分提升胺甲酸酯接著劑硬化膜之密著力且可充分提升在高溫環境下之層壓強度。其中,構成前述外側接著劑層5之甲酸酯接著劑之硬化膜之楊氏模量在140MPa~300MPa之範圍為特佳。此外,前述楊氏模量以JIS K7127-1999為基準測定之楊氏模量。
本發明中,前述金屬箔層4,係擔任賦予包裝材1阻止氧或水分侵入之氣體阻隔性之角色。前述金屬箔層4,並無特別限定,可列舉例如,鋁箔、銅箔,鋁箔為普遍被使用。前述金屬箔層4之厚度在20μm~100μm為佳。藉由在20μm以上,可防止製造金屬箔時之延壓時之針孔產生,且藉由在100μm以下,可減小鼓脹成形、引伸成形等成形時之應力,提升成形性。
前述金屬箔層4,至少內側之面(內側接著劑層6側之面),施加化成處理為佳。藉由施加此種化成處理,可充分防止因內容物(電池之電解液等)腐蝕金屬箔表面。例如藉由以下處理於金屬箔施加化成處理。亦即,例如,於脫脂處理過之金屬之表面,藉由塗工下述1)~3)之中任一者之水溶液後、乾燥,施加化成處理:
1)含有磷酸、鉻酸、及選自氟化物之金屬鹽及氟化物之非金屬鹽所成群中至少1種之化合物
的混合物水溶液;
2)含有磷酸、選自丙烯酸系樹脂、殼聚醣衍生物樹脂及苯酚系樹脂所成群中至少1種之樹脂、及選自鉻酸及鉻(III)鹽所成群中至少1種之化合物的混合物之水溶液。
3)含有磷酸、選自丙烯酸系樹脂、殼聚醣衍生物樹脂及苯酚系樹脂所成群中至少1種之樹脂、選自鉻酸及鉻(III)鹽所成群中至少1種之化合物、及選自氟化物之金屬鹽及氟化物之非金屬鹽所成群中至少1種之化合物的混合物之水溶液。
前述化成皮膜,鉻附著量(單面)在0.1mg/m2~50mg/m2為佳,2mg/m2~20mg/m2為特佳。
前述熱熔著性樹脂層(內側層)3,對於鋰離子蓄電池所使用之腐蝕性強的電解液等,具備優良的耐藥品性,且發揮賦予包裝材熱密封性之作用。
構成前述熱熔著性樹脂層3之樹脂,並無特別限定,例如,可例舉聚乙烯、聚丙烯、離聚物、乙烯丙烯酸乙酯(EEA)、乙烯丙烯酸甲酯(EAA)、乙烯甲基丙烯酸甲酯樹脂(EMMA)、乙烯-乙酸乙烯酯共聚物樹脂(EVA)、馬來酸酐變性聚丙烯、馬來酸酐變性聚乙烯等。
前述熱熔著性樹脂層3之厚度,設定於15μm~30μm為佳。藉由在15μm以上,可確保充分的熱密封強度,且藉由設定在3
0μm以下,促進薄膜化、輕量化。前述熱熔著性樹脂層3,形成為熱熔著性樹脂未延伸薄膜層為佳,前述熱熔著性樹脂層3,可為單層亦可為複層。
前述內側接著劑層(第2接著劑層)6,並無特別限定,例如,使用硬化型接著劑為佳。前述硬化型接著劑,可列舉例如,熱硬化型丙烯酸接著劑、熱硬化型酸變性聚丙烯接著劑、熱硬化型聚胺甲酸酯接著劑等。其中,使用熱硬化型丙烯酸接著劑為佳,此時具有可降低為了促進硬化之加熱老化處理溫度(例如40℃)之優點,藉由如此的降低,可得到充分防止因加熱老化處理產生熱熔著性樹脂層3之白粉的有利效果。前述內側接著劑層6之厚度(乾燥後之厚度),設定於1μm~4μm為佳。
藉由成形(深引伸成形、鼓脹成形等)本發明之包裝材1,可得到外殼(電池外殼)10(參照圖4)。此外,本發明之包裝材1,可不經過成形直接使用(參照圖4)。
使用本發明之包裝材1構成之蓄電裝置30之一實施型態如圖3所示。此蓄電裝置30為鋰離子蓄電池。本實施型態,如圖3、4所示,藉由成形包裝材1而得到外殼10及,未經成形之平面狀包裝材1,構成外裝部材15。因此,成形本發明之包裝材1而得到成形之外殼10之收容凹部內,收容略長方體形狀之蓄電裝置本體部(電化學元件等)31,於該蓄電裝置本體部31之上,本發明之包裝材1未經成形且使其內側層3側為內方(下側)而配置,藉由將該平面狀包裝材1之內側層3之周緣部及,前述成形外殼10之凸緣部(封止用周緣部)29之內側層3以熱密封而密封接合並封止,構成本發明之蓄電裝置30(參照圖3、4)。
此外,前述外殼10之收容凹部之內側之表面成為內側層(熱熔著性樹脂層)3,收容凹部之外面成為外側層(耐熱性樹脂層)2(參照圖4)。
圖3中,39為前述包裝材1之周緣部與前述外殼10之凸緣部(封止用周緣部)29接合(熔著)之熱密封部。此外,前述蓄電裝置30中,連接於蓄電裝置本體部31之接片之前端部,於外裝部材15之外部導出,但圖式中省略。
前述蓄電裝置本體部31,並無特別限定,可列舉例如,電池本體部、電容器本體部等。
前述熱密封部39之寬度,設定於0.5mm以上為佳。在0.5mm以上,可確實地進行封止。其中,前述熱密封部39之寬度,設定於3mm~15mm為佳。
前述實施型態為,外裝部材15,由成形包裝材1而得到之外殼10及,平面狀之外裝材1所形成之構成(參照圖3、4),但並無特別限定於此種組合,例如,外裝部材15,由一對包裝材1所形成之構成亦可,或一對外殼10所形成之構成亦可。
接著,說明關於本發明之包裝材之製造方法。
首先,準備積層物(準備步驟):積層物含有熱水收縮率1.5%~12%之耐熱性樹脂薄膜所構成之耐熱性樹脂層(外側層)2、熱熔著性樹脂層(內側層)3、於其兩層間配置之金屬箔層4;前述熱熔著性樹脂層3及前述金屬箔層4介在硬化型內側接著劑而接著,前述耐熱性樹脂層2及前述金屬箔層4介在含有多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物之熱
硬化型外側接著劑層而接著。
前述多元醇、前述多官能異氰酸酯化合物、前述「1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物」,各自使用何種物質等如同前述。
此外,前述硬化型內側接著劑,並無特別限定,可列舉例如,熱硬化型丙烯酸接著劑、熱硬化型酸變性聚丙烯接著劑、熱硬化型聚胺甲酸酯接著劑等,其中,使用熱硬化型丙烯酸接著劑為佳。
接著,使前述積層物中前述硬化型內側接著劑及前述硬化型接著劑硬化,較佳為藉由前述積層物在37℃~55℃範圍之溫度下進行加熱處理,使前述硬化型內側接著劑及前述硬化型接著劑硬化(老化處理步驟)。經過前述老化處理步驟,可得到本發明之包裝材1。前述加熱處理在38℃~52℃下進行為特佳。
前述加熱處理(加熱老化處理步驟)之時間,並無特別的限定,硬化型內側接著劑使用熱硬化型丙烯酸接著劑時,前述加熱處理進行3日~15日為佳;硬化型內側接著劑使用熱硬化型酸變性聚丙烯接著劑時,前述加熱處理進行3日~15日為佳;硬化型內側接著劑使用熱硬化型聚胺甲酸酯系接著劑時,前述加熱處理進行3日~15日為佳。
接著,說明關於本發明之具體的實施例,但本發明不特別限制於該實施例之物。
<實施例1>
於厚度35μm之鋁箔(JIS H4160所規定之A8
079之鋁箔)4之兩面,塗佈由磷酸、聚丙烯酸(丙烯酸系樹脂)、鉻(III)鹽化合物、水、醇所成之化成處理液後,以180℃下進行乾燥,形成化成皮膜。此化成皮膜之鉻附著量每單面為10mg/m2。
接著,在前述完成化成處理之鋁箔4之一側之面上,塗佈數量平均分子量25000之聚酯多元醇100質量份、甲苯二異氰酸酯(TDI)25質量份、三羥甲基丙烷(TMP)10質量份之熱硬化型外側接著劑,且乾燥後之質量為3.5g/m2。
前述聚酯多元醇為,混合己二酸(脂肪族二羧酸)50莫耳份及間苯二甲酸(芳香族二羧酸)50莫耳份所構成之二羧酸成分、及新戊二醇30莫耳部、乙二醇30莫耳部及1,6-己二醇40莫耳部所構成之多價醇成分,在210℃下進行20小時縮聚合反應而得到之聚酯多元醇。因此,前述二羧酸成分中之芳香族二羧酸之含有率為50莫耳%。
此外,前述熱硬化外側接著劑中,相對於聚酯多元醇之羥基(OH)之莫耳數,甲苯二異氰酸酯(TDI)之異氰酸酯基(NCO)之莫耳數之比率(當量比〔NCO〕/〔OH〕)為10。
另一方面,熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜2之單面上,藉由噴霧塗佈法塗佈混合胺甲酸酯樹脂70質量份、環氧樹脂30質量份之樹脂後,乾燥後形成厚度0.05μm之易接著層8,得到附有易接著層8之2軸延伸聚醯胺薄膜2。前述熱水收縮率2.0%之2軸延伸聚醯胺薄膜2,藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於214℃而得。
前述鋁箔4之一側之面之外側接著劑塗佈面上,重疊前述附
有易接著層8之聚醯胺薄膜2之易接著層側之面貼合。
接著,前述鋁箔4之另一側之面,塗佈熱硬化型酸變性聚丙烯接著劑所構成之內側接著劑且乾燥後之質量為2.5g/m2,該內側接著劑塗佈面上,藉由貼合厚度30μm之未延伸聚丙烯薄膜3,得到積層物。
前述積層物藉由於40℃環境下靜置9日進行加熱老化處理,同時硬化熱硬化型外側接著劑及熱硬化型內側接著劑,形成外側接著劑層5及內側接著劑層6,得到圖2所示構成之包裝材1。
<實施例2>
二羧酸成分,除了使用己二酸(脂肪族二羧酸)40莫耳份及間苯二甲酸(芳香族二羧酸)60莫耳份所構成之二羧酸成分以外,與實施例1相同製法,得到圖2所示構成之包裝材1。
<實施例3>
二羧酸成分,除了使用己二酸(脂肪族二羧酸)30莫耳份及間苯二甲酸(芳香族二羧酸)70莫耳份所構成之二羧酸成分以外,與實施例1相同製法,得到圖2所示構成之包裝材1。
<實施例4>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率5.0%之2軸延伸聚醯胺薄膜以外,與實施例3相同製法,得到圖2所示構成之包裝材1。前述熱水收縮率5.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於191℃而得到。
<實施例5>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率10.0%之2軸延伸聚醯胺薄膜以外,與實施例3相同製法,得到圖2所示構成之包裝材1。前述熱水收縮率10.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於160℃而得到。
<實施例6>
除了熱硬化型外側接著劑中,相對聚酯多元醇之羥基(OH)之莫耳數,甲苯二異氰酸酯(TDI)之異氰酸酯基(NCO)之莫耳數之比率(當量比〔NCO〕/〔OH〕)設定為25以外,與實施例3相同製法,得到圖2所示構成之包裝材1。
<實施例7>
除了將數量平均分子量25000之聚酯多元醇100質量份置換成使用數量平均分子量28000之聚酯多元醇100質量份以外,與實施例3相同製法,得到圖2所示構成之包裝材1。
<實施例8>
除了將甲苯二異氰酸酯(TDI)25質量份置換成使用二苯甲烷二異氰酸酯(MDI)25質量份以外,與實施例3相同製法,得到圖2所示構成之包裝材1。
<實施例9>
除了將三羥甲基丙烷(TMP)10質量份置換成使用乙二醇(EG)6質量份以外,與實施例3相同製法,得到圖2所示構成之包裝材1。
<實施例10>
除了將三羥甲基丙烷(TMP)10質量份置換成使用丙三醇9質量份以外,與實施例3相同製法,得到圖2所示構成之包裝材1。
<實施例11>
除了未設置易接著層8以外,與實施例3相同製法,得到圖1所示構成之包裝材1。亦即,於實施例3,鋁箔4之一側之面之外側接著劑塗佈面上,重疊附有易接著層之聚醯胺薄膜之易接著層側之面貼合;將此置換成,鋁箔4之一側之面之外側接著劑塗佈面上,重疊熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜貼合。
<實施例12>
除了二羧酸成分,使用己二酸(脂肪族二羧酸)70莫耳份及間苯二甲酸(芳香族二羧酸)30莫耳份所構成之二羧酸成分以外,與實施例11相同製法,得到圖1所示構成之包裝材1。
<實施例13>
除了二羧酸成分,使用己二酸(脂肪族二羧酸)70莫耳份及間苯二甲酸(芳香族二羧酸)30莫耳份所構成之二羧酸成分以外,與實施例1相同製法,得到圖2所示構成之包裝材1。
<實施例14>
除了不設置易接著層8,且二羧酸成分,使用己二酸(脂肪族二羧酸)10莫耳份及間苯二甲酸(芳香族二羧酸)90莫耳份所構成之二羧酸成分以外,與實施例6相同製法,得到圖1所示構成之包裝材1。
<實施例15>
除了二羧酸成分,使用己二酸(脂肪族二羧酸)10莫耳份
及間苯二甲酸(芳香族二羧酸)90莫耳份所構成之二羧酸成分以外,與實施例6相同製法,得到圖2所示構成之包裝材1。
<實施例16>
除了未設置易接著層8以外,與實施例1相同製法,得到圖1所示構成之包裝材1。亦即,於實施例1,鋁箔4之一側之面之外側接著劑塗佈面上,重疊附有易接著層之聚醯胺薄膜之易接著層側之面貼合;將此置換成,鋁箔4之一側之面之外側接著劑塗佈面上,重疊熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜貼合。
<實施例17>
除了未設置易接著層8以外,與實施例2相同製法,得到圖1所示構成之包裝材1。亦即,於實施例2,鋁箔4之一側之面之外側接著劑塗佈面上,重疊附有易接著層之聚醯胺薄膜之易接著層側之面貼合;將此置換成,鋁箔4之一側之面之外側接著劑塗佈面上,重疊熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜貼合。
<實施例18>
除了未設置易接著層8以外,與實施例3相同製法,得到圖1所示構成之包裝材1。亦即,於實施例3,鋁箔4之一側之面之外側接著劑塗佈面上,重疊附有易接著層之聚醯胺薄膜之易接著層側之面貼合;將此置換成,鋁箔4之一側之面之外側接著劑塗佈面上,重疊熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜貼合。
<實施例19>
除了未設置易接著層8以外,與實施例6相同製法,得到圖
1所示構成之包裝材1。亦即,於實施例6,鋁箔4之一側之面之外側接著劑塗佈面上,重疊附有易接著層之聚醯胺薄膜之易接著層側之面貼合;將此置換成,鋁箔4之一側之面之外側接著劑塗佈面上,重疊熱水收縮率2.0%、厚度15μm之2軸延伸聚醯胺薄膜貼合。
<比較例1>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例12相同製法,得到包裝材。前述熱水收縮率1.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例2>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例14相同製法,得到包裝材。前述熱水收縮率1.0%之2軸延伸聚醯胺薄膜係,藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例3>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例1相同製法,得到包裝材。前述熱水收縮率1.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例4>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例2相同製法,得到包裝材。前述熱
水收縮率1.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例5>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例3相同製法,得到包裝材。前述熱水收縮率1.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例6>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率1.0%之2軸延伸聚醯胺薄膜以外,與實施例6相同製法,得到包裝材。前述熱水收縮率1.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於221℃而得到。
<比較例7>
除了前述2軸延伸聚醯胺薄膜2,使用熱水收縮率15.0%之2軸延伸聚醯胺薄膜以外,與實施例3相同製法,得到包裝材。前述熱水收縮率15.0%之2軸延伸聚醯胺薄膜,係藉由將聚醯胺薄膜2軸延伸加工時之熱固定溫度設定於135℃而得到。
<比較例8>
除了熱硬化型外側接著劑,使用含有數量平均分子量25000之聚酯多元醇100質量份、甲苯二異氰酸酯(TDI)25質量份之熱硬化型外側接著劑(不含有TMP等之脂肪族化合物)以外,與實施例3相同製法,得到包裝材。
對於前述所得到之各包裝材,基於下述測定法、評價法進行
評價。
<楊氏模量測定法>
實施例、比較例所使用之各外側接著劑熱硬化後所得硬化膜之楊氏模量(MPa)以JIS K7127-1999為基準而測定。具體而言,各外側接著劑於玻璃板上塗佈50μm之厚度後,於40℃下進行老化處理11日,得到熱硬化外側接著劑且厚度46μm之硬化物。前述硬化物從玻璃板剝離後,切成寬15mm×長100mm之大小,製作試驗片,使用島津製作所製拉伸壓縮試驗機(AGS-5kNX),以拉伸速度200mm/分進行前述試驗片之拉伸試驗,測定楊氏模量(MPa)
<成形性評價法>
使用AMADA股份有限公司製之深引伸成形具對包裝材進行縱55mm×橫35mm×各深度之略長方體形狀(1面為開放之略長方體形狀)之深引伸成形,即改變成形深度進行深引伸成形,調查得到之成形體之角落部之針孔及破損的有無,調查不會發生此種針孔及破損之「最大成形深度(mm)」,基於下述判定基準評價。此外,針孔或破損之有無,於暗房以光透過法調查。
(判定基準)
「○」…不會發生針孔及破損之最大成形深度為5mm以上
「△」…不會發生針孔及破損之最大成形深度為4mm以上、低於5mm
「×」…不會發生針孔及破損之最大成形深度為低於4mm。
<密封性評價法>(進行成形深度深的成形有無發生層間剝離之評
價)
成形深度深的成形,使用前述深引伸成形具對包裝材進行縱55mm×橫35mm×5mm之略長方體形狀(1面為開放之略長方體形狀)之深引伸成形。此時,耐熱性樹脂層2成為成形體之外側而進行成形。各實施例、各比較例各別製作2個成形體,使2個成形體10之凸緣部(封止用周緣部;參照圖4)29接觸並重合,170℃×6秒間進行熱密封後,藉由肉眼觀察熱密封部39有無發生層間剝離(剝離)及有無外觀浮動,基於下述判定基準評價。
(判定基準)
「○」…確認沒有層間剝離(剝離)及確認沒有外觀浮動(合格)
「△」…細微的層間剝離(剝離)極少發生,沒有實質上的層間剝離(剝離),亦沒有外觀浮動(合格)
「×」…發生層間剝離(剝離)、外觀亦有浮動(不合格)。
<耐熱水性評價法>(高溫潮濕等嚴苛的環境下使用時之層間剝離發生有無之評價)
使用前述深引伸成形具對包裝材進行縱55mm×橫35mm×5mm之略長方體形狀(1面為開放之略長方體形狀)之深引伸成形。此時,耐熱性樹脂層2成為成形體之外側而進行成形。各實施例、各比較例各別製作2個成形體,2個成形體10之凸緣部(封止用周緣部;參照圖4)29接觸並重合,170℃×6秒間進行熱密封後,接著熱密封物於85℃之熱水中浸漬240小時之後取出,藉由肉眼觀察熱密封部39有無發生層間剝離(剝離)及有無外觀浮動,基於下述判定基準評價。
(判定基準)
「○」…確認沒有層間剝離(剝離)及確認沒有外觀浮動(合格)
「△」…細微的層間剝離(剝離)極少發生,沒有實質上的層間剝離(剝離),亦沒有外觀浮動(合格)
「×」…發生層間剝離(剝離)、外觀亦有浮動(不合格)。
<高溫中的層壓強度測定法>
從得到之包裝材切取出寬15mm×長150mm之試驗體,從此試驗體之長方向之一端至進入內側10mm位置之區域,使鋁箔及耐熱性樹脂層之間剝離。
以JIS K6854-3(1999年)為基準,使用島津製作所製拉伸壓縮試驗機(AGS-5kNX),一側之夾頭夾住固定含有鋁箔之積層體,另一側之夾頭夾住固定前述剝離之耐熱性樹脂層,120℃之溫度環境下維持1分鐘後,繼續在120℃之溫度環境下以拉伸速度100mm/分測定T型剝離時之剝離強度,此測定值之安定狀態之值作為「高溫中的層壓強度(N/15mm寬)」。測定結果基於下述判定基準評價。
(判定基準)
「○」…層壓強度為「2.0N/15mm寬」以上
「△」…層壓強度為「1.5N/15mm寬」以上、低於「2.0N/15mm幅」
「×」…層壓強度為低於「1.5N/15mm寬」。
從表中很明顯地,本發明之實施例1~19之包裝材,即使
進行深度深的成形亦不產生針孔或裂縫而具備優良的成形性,且進行深度深的成形亦能抑制層間剝離(剝離),高溫中亦有大的層壓強度、耐熱水性亦良好,高溫潮濕的嚴苛環境下使用亦能防止層間剝離(剝離)。
相對於此,脫離本發明之申請專利範圍之規定範圍之比較例1~8,至少其中一項之評價為「×」(差)之評價。
本發明之包裝材,適合作為筆記型電腦用、手機用、車載用、固定型之鋰離子聚合物蓄電池等電池之包裝材使用,除此之外,適合作為食品之包裝材、醫藥品之包裝材,但並無特別限定此等用途。其中,特別適合作為電池用包裝材。此外,本發明之包裝材,適合作為成形用包裝材。
本發明之外殼(成形外殼),適合作為筆記型電腦用、手機用、車載用、固定型之鋰離子聚合物蓄電池等電池之外殼使用,但並無特別限定此等用途。其中,特別適合作為電池用外殼。
本申請案,係伴隨著在2015年10月7日提出申請的日本專利申請案的特願2015-199410號的優先權主張,其揭示內容直接構成本申請案的一部分。
在此所使用的用語及說明,係用以說明本發明的實施形態所使用,但本發明並不限定於此。在本發明所揭示且敘述的特徵事項的任何均等物皆不應被排除,且在本發明所請求的範圍內的各種變形亦應被理解為係可被接受的。
1‧‧‧包裝材
2‧‧‧耐熱性樹脂層(外側層)
3‧‧‧熱熔著性樹脂層(內側層)
4‧‧‧金屬箔層
5‧‧‧第1接著劑層(外側接著劑層)
6‧‧‧第2接著劑層(內側接著劑層)
8‧‧‧易接著層
10‧‧‧外殼(成形外殼)
15‧‧‧外裝部材
30‧‧‧蓄電裝置
31‧‧‧蓄電裝置本體部
Claims (10)
- 一種包裝材,其特徵為其係包含外側層之耐熱性樹脂層、內側層之熱熔著性樹脂層、及配置於此兩層間之金屬箔層之包裝材;其中,前述耐熱性樹脂層,係由熱水收縮率為1.5%~12%之耐熱性樹脂薄膜所成,前述耐熱性樹脂層與前述金屬箔層係介由外側接著劑層而接著,前述外側接著劑層,係由聚胺甲酸酯接著劑所形成,且該聚胺甲酸酯接著劑係含有:多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物。
- 如申請專利範圍第1項所記載之包裝材,其中,前述多元醇,係聚酯多元醇。
- 如申請專利範圍第2項所記載之包裝材,其中,前述聚酯多元醇,係包含二羧酸成分,前述二羧酸成分,係含有芳香族二羧酸,且前述二羧酸成分中前述芳香族二羧酸之含有率為40莫耳%~80莫耳%。
- 如申請專利範圍第1~3項中任一項所記載之包裝材,其中,前述脂肪族化合物,係多價醇。
- 如申請專利範圍第1~4項中任一項所記載之包裝材,其中,前述外側接著劑層,係含有選自胺甲酸酯鍵、酯鍵、脲鍵、脲甲酸酯鍵、雙縮脲鍵及醯胺鍵所成群中之至少1種鍵結。
- 如申請專利範圍第1~5項中任一項所記載之包裝材,其中,前述耐熱 性樹脂層與前述外側接著劑層之間係配置有易接著層。
- 如申請專利範圍第6項所記載之包裝材,其中,前述易接著層,係含有選自環氧樹脂、胺甲酸酯樹脂、丙烯酸酯樹脂、甲基丙烯酸酯樹脂及聚乙烯亞胺樹脂所成群中之1種或2種以上樹脂。
- 如申請專利範圍第1~7項中任一項所記載之包裝材,其中,前述胺甲酸酯接著劑之硬化膜之楊氏模量係90MPa~400MPa。
- 一種包裝材之製造方法,其特徵係包含:積層物之準備步驟:前述積層物係包含外側層之耐熱性樹脂層、內側層之熱熔著性樹脂層、及於該兩層間配置之金屬箔層;其中,前述耐熱性樹脂層係由熱水收縮率1.5%~12%之耐熱性樹脂薄膜所成,前述熱熔著性樹脂層與前述金屬箔層係介由硬化型內側接著劑層而接著,前述耐熱性樹脂層與前述金屬箔層係介由硬化型外側接著劑層而接著,且前述硬化型外側接著劑層係多元醇、多官能異氰酸酯化合物、及1分子中具有複數個能夠與異氰酸酯基反應之官能基之脂肪族化合物;及老化處理步驟:藉由將前述積層物在37℃~55℃範圍之溫度下進行加熱老化處理,使前述硬化型內側接著劑及前述硬化型外側接著劑硬化。
- 如申請專利範圍第9項所記載之包裝材之製造方法,其中,前述硬化型內側接著劑,係熱硬化型丙烯酸接著劑。
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JP6862084B2 (ja) * | 2015-10-07 | 2021-04-21 | 昭和電工パッケージング株式会社 | 包装材、ケースおよび蓄電デバイス |
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 |
JP7340323B2 (ja) | 2017-12-27 | 2023-09-07 | 株式会社レゾナック・パッケージング | 蓄電デバイス用外装材及び蓄電デバイス |
CN112912982A (zh) * | 2018-10-24 | 2021-06-04 | 大日本印刷株式会社 | 蓄电器件用外装材料、其制造方法和蓄电器件 |
CN113103682A (zh) * | 2020-01-10 | 2021-07-13 | 昭和电工包装株式会社 | 成型用包装材料 |
CN111341948A (zh) * | 2020-03-16 | 2020-06-26 | 湖北亿纬动力有限公司 | 一种金属箔、其制备方法、电芯封装方法以及电池模组 |
KR20240024039A (ko) * | 2021-06-24 | 2024-02-23 | 도판 홀딩스 가부시키가이샤 | 축전 디바이스용 외장재 |
WO2023136360A1 (ja) * | 2022-01-17 | 2023-07-20 | 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、樹脂組成物、及び蓄電デバイス |
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CA2141715C (en) * | 1994-02-08 | 1999-09-14 | Bruce A. Gruber | Organic solvent free urethane/acrylic polymer laminating adhesive for flexible packaging |
JP3567230B2 (ja) | 1998-10-15 | 2004-09-22 | 昭和電工パッケージング株式会社 | 電池ケース用包材 |
US6423810B1 (en) * | 2001-02-05 | 2002-07-23 | Lord Corporation | High strength, long-open time structural polyurethane adhesive and method of use thereof |
JP2002249745A (ja) * | 2001-02-27 | 2002-09-06 | Mitsui Takeda Chemicals Inc | 2液硬化型無溶剤系接着剤組成物 |
JP5519895B2 (ja) * | 2005-05-27 | 2014-06-11 | 昭和電工パッケージング株式会社 | 電池ケース用包材及び電池用ケース |
JP4380728B2 (ja) | 2007-05-16 | 2009-12-09 | ソニー株式会社 | 積層型包装材料、電池用外装部材および電池 |
CN103097484B (zh) * | 2010-05-17 | 2014-07-30 | 汉高公司 | 适于有机金属催化剂的使用非迁移性阻滞剂的可控固化脂肪族层压粘合剂 |
US9646940B2 (en) * | 2010-12-27 | 2017-05-09 | Konica Minolta, Inc. | Gas barrier film and electronic device |
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JP5962345B2 (ja) * | 2012-08-31 | 2016-08-03 | 大日本印刷株式会社 | 電池用包装材料 |
JP5267718B1 (ja) * | 2012-11-01 | 2013-08-21 | 東洋インキScホールディングス株式会社 | 電池用包装材用ポリウレタン接着剤、電池用包装材、電池用容器および電池 |
JP5578269B1 (ja) * | 2013-02-25 | 2014-08-27 | 東洋インキScホールディングス株式会社 | 電池用包装材用ポリウレタン接着剤、電池用包装材、電池用容器および電池 |
JP6230460B2 (ja) * | 2013-06-17 | 2017-11-15 | 昭和電工パッケージング株式会社 | 成形用包装材 |
JP6469356B2 (ja) * | 2013-07-29 | 2019-02-13 | 昭和電工パッケージング株式会社 | 電池ケース |
JP2015082354A (ja) * | 2013-10-21 | 2015-04-27 | 東洋インキScホールディングス株式会社 | 電池用包装材、電池用容器および電池 |
JP6347613B2 (ja) * | 2014-01-31 | 2018-06-27 | 昭和電工パッケージング株式会社 | 成形用包装材の製造方法 |
JP6247136B2 (ja) * | 2014-02-12 | 2017-12-13 | 昭和電工パッケージング株式会社 | 成形用包装材 |
KR102282648B1 (ko) * | 2014-02-12 | 2021-07-27 | 쇼와 덴코 패키징 가부시키가이샤 | 성형용 포장재 |
JP6626258B2 (ja) * | 2014-04-07 | 2019-12-25 | 昭和電工パッケージング株式会社 | ラミネート外装材の製造方法 |
JP2015199410A (ja) | 2014-04-07 | 2015-11-12 | 日産自動車株式会社 | 電動車両用駆動ユニット |
EP3171424B1 (en) * | 2014-07-16 | 2021-08-25 | Toppan Printing Co., Ltd. | Casing material for electricity storage device and electricity storage device including same |
JP6275014B2 (ja) * | 2014-10-24 | 2018-02-07 | 昭和電工パッケージング株式会社 | 成形用包装材及び成形ケース |
US20180264711A1 (en) * | 2014-12-17 | 2018-09-20 | Unitika Ltd. | Polyamide film and method for producing same |
JP6564188B2 (ja) * | 2015-01-09 | 2019-08-21 | 昭和電工パッケージング株式会社 | 蓄電デバイス用外装体 |
CN114696014A (zh) * | 2015-03-03 | 2022-07-01 | 凸版印刷株式会社 | 蓄电装置用封装材料、及使用其的蓄电装置 |
JP6862084B2 (ja) * | 2015-10-07 | 2021-04-21 | 昭和電工パッケージング株式会社 | 包装材、ケースおよび蓄電デバイス |
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2015
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2016
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KR20170041631A (ko) | 2017-04-17 |
TWI769986B (zh) | 2022-07-11 |
CN115257084A (zh) | 2022-11-01 |
US20240243394A1 (en) | 2024-07-18 |
DE102016219364A1 (de) | 2017-04-13 |
CN106571432A (zh) | 2017-04-19 |
JP6862084B2 (ja) | 2021-04-21 |
KR20230166988A (ko) | 2023-12-07 |
US20170104189A1 (en) | 2017-04-13 |
JP2017071414A (ja) | 2017-04-13 |
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