TWI565594B - 箔之結合方法 - Google Patents

箔之結合方法 Download PDF

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TWI565594B
TWI565594B TW103134530A TW103134530A TWI565594B TW I565594 B TWI565594 B TW I565594B TW 103134530 A TW103134530 A TW 103134530A TW 103134530 A TW103134530 A TW 103134530A TW I565594 B TWI565594 B TW I565594B
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adhesive composition
layer
water
metal foil
aqueous medium
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TW201529327A (zh
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曲朝暉
邁 陳
范林
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羅門哈斯公司
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Description

箔之結合方法
本發明係關於箔之結合方法，尤其關於將金屬箔結合至聚合物膜之方法。
黏著劑組成物之一個重要用途係結合層壓體之層。舉例而言，所欲者往往係提供可將金屬箔結合至聚合物膜之黏著劑組成物。由於安全及環境保護之緣故，所欲者係黏著劑組成物為水載(waterborne)。一種所欲之使用水載黏著劑組成物結合層壓體之層的方法係乾結合層壓製程，其係下述之方法：將該水載黏著劑組成物之層施用至第一基材，隨後主動或被動乾燥該水載黏著劑組成物，再將第二基材帶至與經乾燥之黏著劑組成物接觸，通常係經由熱壓夾(nip)將兩基材配對在一起並形成層壓體。
第2010/0081742號美國專利申請號揭示一種水基染色聚胺酯塗層，其可用於砂粒及其他介質之著色。第2010/0081742號美國專利申請號揭示之塗層係視需要含有交聯劑如，舉例而言，β-(3,4-環氧環己基)乙基三乙氧基矽烷。
所欲者係提供使用水載黏著劑組成物將金 屬箔結合至聚合物膜之方法。尤其所欲者係提供使用水載黏著劑組成物進行乾結合層壓之方法，其中，該第一基材係金屬箔，第二基材係聚合物膜。亦所欲者係能用於此等方法中之水載黏著劑組成物。
下述者係本發明之內容。
本發明之第一方面係將金屬箔結合至聚合物膜上之方法，其係包含下列步驟：(a)將水載黏著劑組成物之層施用至該聚合物膜或金屬箔之表面，(b)乾燥該黏著劑組成物之層，以產生經乾燥之黏著劑層，以及(c)於乾燥之後，將金屬箔或聚合物膜之表面帶至與該經乾燥之黏著劑組成物之層接觸，其中，該水載黏著劑組成物包括：(i)水性介質；(ii)分散於該水性介質中之一種或多種異氰酸酯化合物；以及(iii)分散於該水性介質中之一種或多種官能性矽烷化合物。
本發明之第二方面係水載黏著劑組成物，其係包含：(i)水性介質；(ii)分散於該水性介質中之一種或多種異氰酸酯化合 物；以及(iii)分散於該水性介質中之一種或多種官能性矽烷化合物。
下述者係本發明之詳細說明書。
本文中，除非上下文明確指出者，下列術語係具有指定之定義。
金屬箔係一片長度及寬度各為至少1公分(cm)且厚度為0.5毫米(mm)或更薄的金屬。聚合物膜係一片由有機聚合物作成之材質，其長度及寬度各為至少1cm，且厚度為0.5mm或更薄。
本文中，若組成物於25℃為液體，且含有以該組成物之重量為基準計30重量%或更多之水，則稱該組成物為水載。水載組成物係含有連續之流體介質，離散之液滴或粒子可視需要懸浮於該介質中。該連續之流體介質係含有水，水之量為，以該連續之流體介質的重量為基準計，50%重量或更高。本文中，該連續之流體介質係稱為水性介質。
本文中，係稱水載組成物中含有之除水以外的化合物為分散於該水性介質中。此等化合物可溶解或懸浮或兩者之組合。懸浮之化合物係作為離散之液滴或粒子存在；此等粒子可含有兩種或更多種物質。懸浮之液滴 或粒子係具有重量平均直徑為5奈米(nm)或更大。溶解於該水性介質中之化合物係作為獨立分子而分散。
異氰酸酯係含有一個或多個側鏈異氰酸酯基-NCO的化合物。每分子含有超過一個異氰酸酯基之異氰酸酯係多異氰酸酯。含有恰好兩個異氰酸酯基之異氰酸酯係二異氰酸酯。單體性二異氰酸酯係具有結構OCN-R1-NCO，其中，-R1-係不具有異氰酸酯基之二價有機基團，單體性二異氰酸酯不具有胺基甲酸酯鏈結，且具有低於500之分子量。
多元醇係每分子具有兩個或更多個-OH基團的化合物。二元醇係每分子具有恰好兩個-OH基團。
本文中，著色劑係任何染料或顏料。著色劑可係有機或無機或其組合。
本發明之黏著劑組成物係包含水性介質。較佳地，該水性介質中水的量為，以該水性介質之重量為基準計，70重量%或更多；或80重量%或更多；或90重量%或更多。
本發明之黏著劑組成物係含有一種或多種異氰酸酯化合物。較佳地，該黏著劑組成物係含有一種或多種多異氰酸酯。較佳之多異氰酸酯係一種或多種胺基甲酸酯預聚物、一種或多種異氰酸酯三聚物、及其混合物。
異氰酸酯三聚物係單體性二異氰酸酯之三聚物。較佳係經親水修飾之異氰酸酯三聚物，其係具有結構： 其中，三個R基團係彼此相同，且G係含有至少一個親水性基團之有機基團。較佳之R基團係脂族；更佳係正己基及二甲基環己基；更佳係正己基。較佳之親水性基團係陰離子性基團及親水性環氧烷基團；更佳係親水性環氧烷基團。較佳之親水性環氧烷基團係-(CH2CH2O)n-，其中n係3至50。陰離子基團中，較佳係硫酸根及羧酸根；更佳係硫酸根。
胺基甲酸酯預聚物係一種或多種多異氰酸酯與一種或多種多元醇或一種或多種聚胺或其混合物的反應產物。於胺基甲酸酯預聚物之製作中，係使用莫耳過量之多異氰酸酯，且該胺基甲酸酯預聚物係多異氰酸酯。對於作成胺基甲酸酯預聚物，較佳之聚異氰酸酯係具有分子量為300或更低，更佳275或更低的單體性二異氰酸酯。對於製作胺基甲酸酯預聚物，較佳之多異氰酸酯係芳族單體性二異氰酸酯；更佳係MDI之一種或多種異構物；更佳係4,4'-MDI及4,4'-MDI與MDI之其他異構物的混合物；更佳係4,4'-MDI。對於製作胺基甲酸酯預聚物，一種或多種多異氰酸酯較佳係與一種或多種多元醇反應。較佳之多元醇係具有重量平均分子量為500或更高；更佳800或更高。較佳之多元醇係具有重量平均分子量為5,000或更低；更 佳2,500或更低。於該胺基甲酸酯預聚物之製作中，較佳係不使用重量平均分子量小於800之多元醇。較佳之多元醇係二元醇。較佳之多元醇係聚醚多元醇、聚酯多元醇、及其混合物；更佳係聚醚多元醇。較佳之聚醚多元醇係聚四亞甲基醚二醇、聚丙二醇、及其混合物。
較佳之胺基甲酸酯預聚物係製備為聚胺酯分散液，其係組成物，其中，胺基甲酸酯預聚物之粒子係懸浮於水性介質中。
本發明之組成物係含有一種或多種官能性矽烷。官能性矽烷係具有下述結構之化合物： 其中，A係胺基、環氧基、甲基丙烯醯基、乙烯基、巰基、脲、或異氰酸酯基。基團-R1-係二價有機基團。較佳地，-R1-係烴基；更佳係烷基；更佳係線性烷基；更佳係具有1個至6個碳原子之線性烷基；更佳係具有2個至4個碳原子之線性烷基。-R2、-R3、及-R4係各自獨立為-O-R5或-R6，其中，-R5與-R6係各自獨立為烷基；較佳係具有1個至6個碳原子之烷基；更佳係甲基、乙基、或異丙基；更佳係甲基或乙基。較佳地，-R2、-R3、及-R4之一者或多者係-O-R5；更佳地，-R2、-R3、及-R4之兩者或更多者為-O-R5。較佳地，-R2、-R3、及-R4之兩者或更多者係彼此相同。
環氧基團係含有環氧化物環之任何基團。環氧基團係包括，例如，環氧醚基團及β-(3,4-環氧環己基)。環氧醚基團係具有結構； 較佳地，A-係環氧醚、胺基、或巰基。
較佳地，該官能性矽烷係可溶於水中或可懸浮於水中。本文中，若於25℃於介於1與7之間之一個或多個pH值下，以水之重量為基準計，可溶解於水中之官能性矽烷的量為2重量%或更多，則認為該官能性矽烷係可溶於水中。本文中，無論官能性矽烷被認為可溶於水中與否，於該官能性矽烷之溶解形式中，-OR5基團之一者或多者係轉變為-OH基團。本文中，若2公克或更多之官能性矽烷可於25℃懸浮於100公克水中以形成懸浮液，且該懸浮液於25℃存儲24小時後並不沉降或凝集，則認為該官能性矽烷為可懸浮。
較佳地，該水載黏著劑組成物並不含任何著色劑。亦即，該水載黏著劑組成物或完全不含著色劑，或以該組成物之總重為基準計，其含有之著色劑的量為0.1重量%或更少。本文中，以水載黏著劑組成物之總重為基準計，若該組成物含有之著色劑的量係0.1重量%或更少，則因該組成物將含有如此小量之著色劑而該著色劑之量視為可忽略，且可將該組成物視為等同於不含任何著色劑之組成物。
該水載黏著劑組成物係視需要含有一種或多種非胺基甲酸酯聚合物。較佳之非胺基甲酸酯聚合物係乙烯基聚合物，其係含有乙烯系不飽和單體之聚合單元的聚合物。更佳之非胺基甲酸酯聚合物係含有一種或多種丙烯酸系單體、一種或多種乙烯基芳族單體、或其組合的聚合單元。丙烯酸系單體為丙烯酸、甲基丙烯酸、其酯及其醯胺。乙烯基芳族單體係包括苯乙烯及經取代苯乙烯。
當存在一種或多種非胺基甲酸酯聚合物時，此等聚合物之較佳形式係呈懸浮於水性介質中的粒子。
較佳地，該水載黏著劑組成物並不含有任何含任何乙烯基矽烷單體之任何聚合單元的乙烯基聚合物。乙烯基矽烷單體係於其分子中具有可聚合之碳-碳雙鍵及一個或多個矽原子的單體。
於本發明之實踐中，較佳係將水載黏著劑組成物層施用至金屬箔或聚合物膜之表面。更佳係將水載黏著劑組成物層施用至金屬箔之表面上。該金屬箔較佳係鋁箔。該金屬箔之厚度較佳係1微米(μm)或更厚；更佳係3μm或更厚。該金屬箔之厚度較佳係25μm或更薄；更佳係15μm或更薄。
較佳係令水載黏著劑組成物主動或被動乾燥，以形成經乾燥之黏著劑組成物層。可藉由任何方法，包括，舉例而言，時間流逝、施用熱、及曝露於流動空氣之一者或多者而實施乾燥。當該黏著劑組成物層中剩餘之水的量為，以作為該水載黏著劑組成物之部分而施用之水 的重量為基準計，10重量%或更少時，則認為該黏著劑組成物乾燥。
較佳係將經乾燥之該黏著劑組成物層帶至與聚合物膜或金屬箔之表面接觸。更佳係將經乾燥之該黏著劑組成物層帶至與聚合物膜之表面接觸。較佳係使用令兩種基材配對在一起並形成層壓體之熱壓夾而將經乾燥之該黏著劑組成物層帶至與聚合物膜或金屬箔之表面接觸。
該聚合物膜之較佳之聚合物係有機聚合物及金屬化有機聚合物；更佳係聚烯烴、聚烯烴共聚物、聚酯、聚碳酸酯、聚醯胺、及其金屬化膜。聚烯烴係烯烴類單體之均聚物及共聚物，烯烴類單體係含有一個或多個碳-碳雙鍵之烴類分子。聚烯烴共聚物係一種或多種烯烴單體與一種或多種醋酸乙烯酯、丙烯酸酯單體、及甲基丙烯酸酯單體的共聚物。較佳之聚合物係聚乙烯、聚對苯二甲酸乙二酯、及尼龍；更佳係聚乙烯。
於該聚合物膜與經乾燥之該黏著劑組成物接觸之後，較佳係令由是形成之復合物件經受機械力，以將該聚合物膜與該金屬箔朝向彼此壓合。此機械力較佳係藉由令該復合物件於輥間穿過而施加。
於本發明之某些具體態樣中，由該金屬箔、該黏著劑組成物層、及該聚合物膜作成之復合物件係含有其他層之較大復合物件的一部分。該等其他層可含有一層或多層聚合物膜、一層或多層黏著劑組成物層、及一層或多層金屬箔；存在於該等其他層中之任何聚合物膜、 黏著劑組成物、或金屬箔可彼此相同或不同，亦與存在於上揭之復合物件中的聚合物膜、黏著劑組成物、及金屬箔不同。
舉例而言，於某些具體態樣中，較大之復 合物件係如下述者作成。將第一黏著劑組成物之層施用至聚對苯二甲酸乙二酯膜上，將該第一黏著劑組成物帶至與金屬箔之一表面接觸。隨後，將第二黏著劑組成物之層施用於該金屬箔之相反表面上，並將該第二黏著劑組成物帶至與聚乙烯之聚合物膜表面接觸。較佳地，於此等態樣中，第一黏著劑組成物之層與第二黏著劑組成物之層兩者皆為本發明之水載黏著劑組成物之層，且較佳係在與下一基材接觸之前將每一層乾燥。
[實施例]
下文係本發明之實施例。
下列組分係用於該等實施例中：
SPU1+Cat F=AdcoteTM 545-75EA(「SPU1」)加上催化劑F(「Cat F」)係來自陶氏化學公司(Dow Chemical Company)之兩成分溶劑系黏著劑產品
「乳膠L」係ROBONDTM L-168A，來自陶氏化學公司之水性乳膠共聚物；含有一種或多種丙烯酸系單體之聚合單元
異氰酸酯1=ROBONDTM COREACTANT CR3A，來自陶氏化學公司之水可分散性脂族異氰酸酯三聚物
PTMEG1=TetrathaneTM 2000，聚四亞甲基醚二醇，MW= 2000，來自英威達(Invista)
PPG1=VaranolTM V 9287A，聚丙二醇，MW=2000，來自陶氏化學公司
PEG1=CarbowaxTM PEG1000，聚乙二醇，分子量1000，來自陶氏化學公司
MPEG1=CarbowaxTM MPEG 1000，甲氧基聚乙二醇，分子量1000，來自陶氏化學公司
MDI=IsonateTM 125M，來自陶氏化學公司
Surf1=RhodacalTM DS4界面活性劑，十二烷基苯磺酸鈉，來自羅地亞(Rhodia)
箔膜係7μm鋁箔，由中國本土供應商提供
Ny係尼龍膜，15μm厚度
PET係聚對苯二甲酸乙二酯膜，12μm厚度
PE係聚乙烯膜，50μm厚度
矽烷1=SilquestTM A1100，γ-胺基丙基三乙氧基矽烷，由邁圖(Momentive)提供
矽烷2=SilquestTM A189，巰基-丙基三甲氧基矽烷，由邁圖提供
矽烷3=SilquestTM A187，γ-(2,3-環氧基丙氧基)丙基三甲氧基矽烷，由邁圖提供
DI水係去離子水
組分係如下述者用於實施例中。「Comp.」係意指比較性，「Ex.」係意指實施例，「Ingr.」係意指組分， 且「No.」係意指編號。
為了製作實施例1、實施例2及比較性實施例10，於氮氣吹掃下，將編號1至編號4之組分加入1公升之玻璃瓶中。隨後加入編號5及編號7之組分(若使用)，將該瓶緩慢加熱至約80℃。將該瓶於80℃保持2至3小時；檢查NCO含量，維持該溫度直至達到NCO含量之理論值。將所得預聚物置於塑膠瓶中，並使用考爾斯刀片(Cowles blade)以約3000轉/分鐘(rpm)攪拌。隨後加入編號9之組分，再加入冷溫度(5℃)之編號8之組分置於塑膠罐中，高速攪拌以確保達成均質之水包油分散液，然後將編號6之組分緩慢加入該分散液中，繼續攪拌以產生安定之分散液。對於實施例2及比較性實施例10，係使用磁力攪 拌棒攪拌該分散液，同時逐滴加入編號10之組分；隨後繼續攪拌30分鐘。
對於實施例3、4、5、6、7及8、比較性實施例9及比較性實施例11，係使用磁力攪拌棒將上文顯示 之組分混合。
對於每一實施例，係使用K101控制塗覆器(R K PrintCoat Instruments Ltd.)將該黏著劑混合物塗覆於第一基材上，以給出2.3公克(g)/平方公尺(m2)之乾燥塗覆重量。將經塗覆之基材於80℃之烘箱內放置30秒至2分鐘以移除水分。將第二基材帶至與經乾燥之黏著劑接觸，使用熱輥層壓器HL-101(ChemInstruments,Inc.)於約68℃之夾溫度形成層壓體。將層壓樣本於約23℃存儲3至7，隨後藉由兩種不同之測試方法測試其黏著強度：結合強度及蒸煮強度(boiling strength)。
於結合強度測試中，切割15毫米(mm)寬之條帶，隨後使用拉伸測試儀以25cm/分鐘(min)之速率剝離。以牛頓(N)為單位記錄並報導峰值剝離力。失敗模式係記錄如下：
FF：膜失敗，無膜拉伸(基材斷裂而無拉伸)
FT：膜拉伸後撕裂(基材伸長且也斷裂)
於袋內蒸煮(Boil-in-Bag)測試中，將固化之層壓體切割為8cm X 12cm尺寸，使用HSG-C加熱密封儀(Brugger Feinmeehanik GmbH)於140℃及300N/15mm壓力下處理1秒而作成其內具有去離子水之袋子。避免水潑濺於熱密封區域上。使用不可磨滅之標記物標記該熱密封區域或層壓區域內任何可見之預先存在的裂縫。隨後，將該等袋小心地置於沸水中，並於沸水中停留30min，確保全部袋子在整個蒸煮過程中一直浸沒於水中。當完成時，記 錄與預先存在之裂縫相比的隧穿、去層壓或裂解程度。通過測試之樣本將不顯示超過任何預先存在之熱密封或層壓裂縫的隧穿、去層壓或裂解的證據。隨後打開袋子，倒空袋子，令其冷卻，隨後切割為15mm寬之條帶，以使用InstronTM 5943機器測試於25cm/min速度下的T-剝離強度。
測試結果如下。「Ex.」係實施例，「Comp.」係比較性，而「nt」係意指未測試。其中，失敗模式未顯示，該失敗模式係黏著失敗(當該黏著劑於該等基板之一者上的結合失敗或黏著劑被剝離時(其中，該黏著劑層剝離)，則樣本失敗)。
結合強度(牛頓及失敗模式)
袋內蒸煮(牛頓及失敗模式)
結合強度(牛頓及失敗模式)
袋內蒸煮(牛頓及失敗模式)
對於第一基材為箔且第二基材為PE之層壓體，其結果尤為重要。本發明之實施例全部表現得比水載比較性實施例更佳。亦測試溶劑系比較性實施例(comp.Ex.11)，以提供基於非水載之黏著劑能力的製劑。
對於全部其他基材，本發明之實施例係證實有用水準之黏著強度。

Claims (5)

  1. 一種將金屬箔結合至聚合物膜之方法，其係包含下列步驟：(A)將水載黏著劑組成物之層施用至該金屬箔之表面，(B)乾燥該黏著劑組成物之層，以製造經乾燥之黏著劑層，以及(C)於乾燥之後，將聚合物膜之表面帶至與該經乾燥之黏著劑組成物之層接觸，其中，該水載黏著劑組成物係包含：(i)水性介質；(ii)分散於該水性介質中之一種或多種異氰酸酯化合物；以及(iii)分散於該水性介質中之一種或多種官能性矽烷化合物。
  2. 如申請專利範圍第1項所述之方法，其中，該聚合物膜係聚烯烴。
  3. 如申請專利範圍第1項所述之方法，其中，該一種或多種異氰酸酯化合物係包含一種或多種胺基甲酸酯預聚物，其中，該胺基甲酸酯預聚物係包含4,4'-MDI與一種或多種多元醇之反應產物。
  4. 如申請專利範圍第1項所述之方法，其中，該一種或多種異氰酸酯化合物係包含一種或多種經親水修飾之異氰酸酯三聚物。
  5. 如申請專利範圍第1項所述之方法，其中，該水載黏著劑組成物係額外包含一種或多種非胺基甲酸酯聚合物，其係包含作為聚合單元之一種或多種丙烯酸系單體。
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AR097871A1 (es) 2016-04-20
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US20160257796A1 (en) 2016-09-08
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EP3030621A4 (en) 2017-04-26
RU2638394C2 (ru) 2017-12-13
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