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TW201400569A - 整合性熱熔黏膠封裝膜及其用途 - Google Patents

整合性熱熔黏膠封裝膜及其用途 Download PDF

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TW201400569A
TW201400569A TW102117432A TW102117432A TW201400569A TW 201400569 A TW201400569 A TW 201400569A TW 102117432 A TW102117432 A TW 102117432A TW 102117432 A TW102117432 A TW 102117432A TW 201400569 A TW201400569 A TW 201400569A
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melt adhesive
hot melt
encapsulating film
film
package
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TWI563047B (en
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Jin-Yu Chen
Yuhong Hu
Darshak Desai
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Henkel Corp
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Abstract

本發明揭示用於囊封熱熔黏膠之基於丙烯聚合物之封裝膜。該等封裝膜在熔化階段期間易於與各種熱熔黏膠化學品混溶，而不會有害地影響黏膠性質，此使得該封裝膜尤其適用於將熱熔黏膠封裝為枕狀、圓柱狀、袋狀、塊狀、筒狀及類似形式。

Description

整合性熱熔黏膠封裝膜及其用途
本發明係關於用於囊封熱熔黏膠之封裝膜。該等封裝膜在黏膠熔化階段期間易於與該熱熔黏膠混溶，而不會有害地影響黏膠性質，此使得該封裝膜尤其適用於將熱熔黏膠封裝為枕狀、圓柱狀、袋狀、塊狀、筒狀及諸如此類。
熱熔黏膠於室溫下係固體，但其一般以熔化態或液態施加。通常，此等黏膠係以塊狀物形式提供且由於其膠黏性，該等固體黏膠塊不僅彼此黏著或黏附至機械處置裝置，而且亦在運輸期間沾黏灰塵及其他污染物。另外，除非在裝運期間進行支撐，否則某些需高黏性調配物之應用導致將變形或冷流之塊狀物。
已研發封裝熱熔黏膠之各種方法以解決上述問題。在一種方法中，將無黏性粉末施加於熱熔黏膠上，且將內容物包裝於封裝膜中。在某些應用中，在熔化熱熔黏膠之前必須移除封裝膜。在其他方法中，且如美國專利第5,373,682號及美國專利第7,350,644號所教示，封裝膜係熱熔黏膠之一部分，且在熔化階段期間封裝膜與黏膠一起溶解。儘管因其量較少(通常低於總重量之5wt%)，此等膜可能不會有害地影響黏膠性質，但在加熱及應用階段期間該等膜可能不易於摻和於熔化熱熔黏膠中。封裝膜之不混溶部分藉由漂浮於熔體表面上及/ 或黏附於熔化槽之壁而作為不同且單獨一層與熱熔黏膠分離，且隨時間流逝，可造成黏膠熔化槽之機械問題。由於存在基於各種化學品之眾多類型之熱熔黏膠，故必須選擇封裝膜以確保與所選熱熔黏膠之良好可混溶性。
業內仍需要允許用於更廣泛適用性之熱熔黏膠之熱熔黏膠封裝膜。本發明滿足此需要。
本發明提供用於各種熱熔黏膠之整合性封裝膜。無需移除該整合性封裝膜，此乃因在黏膠熔化階段期間該整合性封裝膜易於與熱熔黏膠混溶，而不會不利地影響黏膠性質。
申請者已發現，封裝膜之化學性質、熔體黏度、熔體強度、峰值熔化溫度、偏移熔化溫度及儲存模數之特定組合對於形成適用於各種熱熔黏膠化學品之整合性熱熔黏膠封裝中之化學相容、混溶膜至關重要。
在一實施例中，整合性封裝膜包括丙烯含量為至少70wt%之聚合物摻合物；且該封裝膜具有(a)在200℃下，黏度範圍為約200,000cps至3,000,000cps；(b)熔化峰值溫度範圍為約90℃至140℃；(c)Tm偏移溫度低於149℃；及(d)在100℃下，儲存模數(G’)為約1×106帕斯卡至1×108帕斯卡。
另一實施例係關於一種物件，其係由整合性封裝膜囊封之熱熔黏膠。當整合性封裝膜以最高該物件總重量之2%存在時，該封裝膜在149℃或更高下無需任何攪拌即可與熱熔黏膠完全混溶。該熱熔黏膠包括聚-α-烯烴、橡膠、苯乙烯嵌段共聚物、乙烯-乙酸乙烯酯、乙烯-乙酸丁酯及/或其混合物。該整合性封裝膜包括聚合物摻合物其包括至少70wt%之丙烯含量；並且該封裝膜具有(a)在200℃下，黏度範圍為約200,000cps至3,000,000 cps；(b)熔化峰值溫度範圍為約90℃至140℃；(c)Tm偏移溫度低於149℃；及(d)在100℃下，儲存模數(G')為約1×106帕斯卡至1×108帕斯卡。
再一實施例係關於一種利用封裝膜封裝熱熔黏膠以形成整合性熱熔黏膠封裝之方法。該製程包括以下步驟：(1)將整合性封裝膜製成囊封容器；(2)將熔化態之熱熔黏膠泵送或傾倒於整合性封裝膜中，並且該整合性封裝膜與散熱器直接接觸；(3)密封整合性封裝膜；及(4)冷卻密封封裝。該整合性封裝膜包括聚合物摻合物，其包括(a)約70wt%至約99wt%之丙烯含量及(b)約1wt%至約30wt%之丁烯及/或乙烯含量。該整合性熱熔黏膠係在運輸期間耐灰塵及其他污染物之密封、無黏性封裝。
本文所用術語「烯烴熱熔黏膠」通常係指所有基於聚烯烴之熱熔黏膠，包含(但不限於)由非晶形烯烴、聚乙烯、聚丙烯、聚丁烯及其共聚物製成之熱熔黏膠。
本文所使用術語「包裹」、「囊封」及「封裝」可互換使用且意指將熱熔黏膠塊包裝於一層膜內。該膜係無黏性或無結塊層且進一步用以保護黏膠免於污染，用以允許容易的運送及處置。
文中所使用術語「整合性封裝膜」係圍繞熱熔黏膠塊之封裝膜，且可在加熱及應用黏膠期間處理(熔化並應用於基板上)而無需移除膜。類似於經封裝膜，該整合性封裝膜亦無結塊且保護黏膠免於污染。
該整合性封裝膜包括聚合物摻合物。該聚合物摻合物包括至少兩種熱塑性聚合物，且該摻合物之丙烯含量基於聚合物摻合物之總重 量為至少約70wt%，且高達約99wt%。富丙烯共聚物之實例為Idemitsu Kosan有限公司之LMPP400、LMPPS600；ExxonMobile公司之Linxar 127、Vistamaxx 6202、Vistamaxx 6102、Vistamaxx 3980、Vistamaxx 3020、Vistamaxx 3000；及諸如此類。
在一實施例中，其他熱塑性聚合物係丁烯及/或乙烯共聚單體。其他熱塑性聚合物基於聚合物摻合物之總重量可佔約1wt%至約30wt%。乙烯基於聚合物摻合物之總重量可佔最高15wt%，較佳低於10wt%。適宜之市售富丁烯聚合物包含Evonik Industries之Vestoplast 308、Vestoplast 408、Vestoplast 508、Vestoplast 520、Vestoplast 608、Vestoplast 703及諸如此類。適宜之市售富乙烯聚合物包含Dow Chemicals之Affinity GA1950及諸如此類。
至少一種熱塑性聚合物係茂金屬催化之聚合物。適宜之聚合物包含茂金屬催化之聚乙烯、乙烯-丁烯及乙烯-辛烷彈性體、塑性體、丙烯-丁烯、丙烯-乙烯共聚物。
若需要，該等膜可含有用以增強穩定性之抗氧化劑以及其他可選組份，包含滑動助劑(例如芥酸醯胺)、抗結塊劑(例如矽藻土)、脂肪醯胺或其他處理助劑、抗靜電劑、穩定劑、增塑劑、染料、香料、填料(例如滑石粉或碳酸鈣)及諸如此類。
聚合物摻合物可藉由業內已知之任一方式摻和。在一實施例中，該聚合物摻合物係在雙螺桿擠出機中進行混合及熔化處理。然後該熔化摻合物可用業內已知之任一方式澆鑄成膜。膜厚度通常應將在約0.5mil至約5mil間變化，較佳為約1mil至約3mil。特定膜之厚度亦視組合物及應用溫度而變。該膜可為單層或多層膜。
已發現，該封裝膜必須具有某些性質之特定組合以形成整合性熱熔黏膠封裝，該封裝與各種熱熔黏膠化學品化學相容且同時維持作為用於熱熔黏膠之封裝膜之完整性。此封裝膜需要(a)在200℃下，黏 度範圍為約200,000cps至3,000,000cps；(b)峰值熔化溫度(Tm)範圍為約90℃至140℃；(c)熔化溫度(Tm)偏移溫度低於149℃；以及(d)在100℃下，儲存模數(G’)範圍為約1×106帕斯卡至約1×108帕斯卡。
峰值熔點及偏移可藉由業內已知之各種方法測定。所報告之峰值熔點及本文所報告之Tm偏移值係利用DSC(差示掃描量熱法)測定。除非另有說明，否則將約5mg膜樣品密封於壓接氧化鋁盤中，將樣品冷卻至-40℃，且然後利用2920 DSC TA儀器以10℃/min之速率將其再加熱至180℃。使用第二加熱循環之吸熱熔化峰評估峰值熔點及熔融熱，且熔化峰之末端為Tm偏移溫度。
該封裝膜必須涵蓋所有上述性質以形成封裝膜，在囊封熔化黏膠的同時維持該膜之完整性，產生用於熔化黏膠之無黏性障壁密封而且在熔化時無需任何攪拌即與熱熔黏膠一起完全溶解。該封裝膜在高溫(模擬箱車條件之溫度(35-45℃))下無結塊。該封裝膜在高於約149℃之溫度下無需任何攪拌或額外能量即可在5小時內熔化。該封裝膜可與各種及多種熱熔黏膠一起熔化，且可摻和於熔化熱熔黏膠中而不會有害地影響黏膠性質。
另一實施例係關於一種物件，其包括用封裝膜包裝之熱熔黏膠。該物件係形成為枕狀、圓柱狀、袋狀、塊狀、筒狀或鰷魚狀(chub)之整合性熱熔黏膠封裝。
該整合性熱熔黏膠封裝之熱熔黏膠包括各種熱塑性聚合物。熱熔黏膠主要由聚合物構成，該等聚合物包含聚-α-烯烴、橡膠、苯乙烯嵌段共聚物、乙烯-乙酸乙烯酯、乙烯-乙酸丁酯及/或其混合物。該熱熔黏膠可視情況包括增黏劑、增塑劑、油、蠟及添加劑。
在一實施例中，封裝膜佔整合性熱熔黏膠封裝之最多約2重量%，且較佳約0.1%至約1.5%，以防止過度稀釋黏膠性質。通常，每一封裝膜之厚度範圍為約0.5mil至約5mil，較佳為約1mil至約3mil。
整合性熱熔黏膠封裝之封裝膜與各種熱熔黏膠混溶，而該膜之任何部分均不會因漂浮於熱熔體表面上或黏附至熔化槽之壁而與熔化熱熔黏膠分離。
通常，為形成混溶、化學相容且不分離之黏膠，封裝膜係基於熱熔黏膠中所使用之主要聚合物來選擇。未能選取相容之熱熔黏膠及封裝膜導致部分膜漂浮於熱熔體表面上或黏附至熔化槽之壁。已發現，本發明之封裝膜可與多種熱熔黏膠化學品混溶，例如，聚烯烴、橡膠、乙烯-乙酸乙烯酯共聚物、聚醯胺、聚酯、聚胺基甲酸酯及諸如此類，同時形成非黏性外部保護。
為用封裝膜封裝熱熔黏膠，將熱熔黏膠熔化並泵送或傾倒於圓柱形熱塑性膜中，其中圓柱形管與散熱器(例如，冷卻水或冷卻液或氣態環境)直接接觸。包覆及密封該膜可以手動方式或更佳藉由自動程序發生。熱熔黏膠在傾倒或泵送時處於或高於封裝膜熔點之溫度，且封裝膜內部開始與熔化熱熔黏膠一起熔化並摻和於熔化黏膠中而不會有害地影響黏膠性質。將熔化熱熔黏膠填充之圓柱體密封並使其凝固。視情況，在密封過程中利用真空移除空氣，且因此膜與熱熔黏膠之間不存在任何間隙。所得個別地整合性熱熔黏膠封裝可經儲存、處置及使用，即使暴露於升高之壓力及/或溫度下亦不會出現個別包裝黏結在一起、黏附至其他物件或被污染之情況。
為最終利用整合性熱熔黏膠封裝作為黏膠，將封裝置於熔化槽中而無需移除膜。熱熔黏膠與整合性封裝膜間之強界面或中間相需要極少之額外能量即可將膜熔化並摻和於黏膠自身中。
實例 實例1
樣品1至7形成為封裝膜。丙烯(PP)及丁烯/乙烯共單體含量列示於表1中。黏度係在200℃下利用流變儀以接近零剪切量測。該等膜係 藉由將聚合物組份熔化穿過雙螺桿擠出機，且然後將其於冷軋輥上澆鑄至厚度1.5mil形成。膜之可混溶性係藉由在熔化槽中在160℃下熔化約10,000克非晶形聚α-烯烴黏膠(Henkel公司之DISPOMELT® LITE 300)及約0.5wt%(以黏膠計)膜樣品評估。在無任何攪拌之情況下，記錄膜樣品熔化於黏膠中所需之時間長度。對於樣品8，亦採用具有3% VA含量之EVA吹塑膜用於此研究。
N/A-不可用
在200℃下具有小於200,000cps之低熔體黏度的膜樣品1無法轉化成膜。所有其他樣品，即膜樣品2至8皆澆鑄成膜。
不到3小時膜樣品2至6即熔化於DISPOMELT® LITE 300中且形成均質體。膜樣品7亦形成均質體，但非茂金屬基聚丙烯共聚物膜耗費5小時以上方變得與非晶形聚α烯烴型熱熔黏膠混溶。EVA膜(即膜樣品8)耗費超過24小時熔化於黏膠中。此外，EVA膜膠凝並形成硬團簇，且一些硬團簇漂浮於熱熔化槽表面上。此類硬團簇係不合意的，因其 易於堵塞噴霧式或槽縫式噴嘴。
實例2
表徵樣品膜之熔化溫度及熔化模數用以評價其熔化強度，且結果顯示於表2中。熔點係以2920 DSC(差示掃描量熱法)TA儀器測定。將約5mg至10mg樣品密封於壓接氧化鋁盤中，冷卻至-40℃，且利用2920 DSC TA儀器以10℃/分鐘之速率將其再加熱至180℃。使用第二加熱循環以評估峰值熔點及Tm偏移值。
膜在100℃下之儲存模數(G’)係藉由流變動態分析儀(Rheometric Dynamic Analyzer,RDA III)及TA Orchestrator軟體(版本7.2.0.2)測定。將黏膠樣品加載於直徑7.9mm之平行板中並間隔約2mm間隙。然後將樣品冷卻至約-30℃，並啟動時間程式。程式測試之溫度以5℃之間隔升高，隨後係在每一溫度下10秒之熱煉時間。用氮氣連續地沖洗含有樣品之對流烘箱。頻率保持在10rad/s。測試開始之初始應變為0.05%(在板之外邊緣)。軟體中之自動應變(autostrain)選項係用以在整個測試中維持準確地可量測扭矩。該選項經組態以便軟體所允許之最大施加應變係30%。自動應變程式調整在每一溫度增量下之應力。藉由軟體依據扭矩及應變數據計算剪切儲存或彈性模數(G')。
藉由用膜樣品囊封熔化DISPOMELT® LITE Lite 300以形成封裝來評估膜樣品之膜強度。冷卻後，目測評估黏膠封裝之品質及強度。若膜樣品維持完整性且形成熱熔黏膠之外殼，則該膜給予等級「強」。若存在任何孔或熱熔黏膠破壞膜樣品之完整性，則該膜給予等級「弱」。
樣品1至3在填充過程中破裂，導致不可接受之封裝。樣品4至8足夠強而形成樣品膜無任何破裂之可接受封裝。已發現，峰值Tm範圍在約90℃至140℃及在100℃下儲存模數為約1×106帕斯卡至約1×108帕斯卡使得膜承受填充過程並產生品質可接受之封裝。
實例3
使用樣品4至8測試其噴霧性。用厚度為約1.5mil之樣品膜囊封約10,000g之DISPOMELT LITE® Lite 300黏膠樣品。將黏膠封裝加載於設定為160℃之熔化槽中且對於樣品4至6持續3小時(樣品7為10小時，且樣品8為24小時)。然後將熔化黏膠噴霧穿過四埠ITW噴頭(Nordson)並將雜散糰粒/分鐘之數目記錄於表3。每一樣品膜之Tm偏移亦記錄於表3中。
樣品7具有大於10個雜散糰粒/分鐘之值。相比之下，樣品4至6僅具有2個雜散糰粒/分鐘。與樣品7不同，樣品4至6之Tm偏移值低於149℃。已發現，封裝膜之Tm偏移值低於149℃係最小化噴霧性中雜散之重要因子。雖然樣品8之Tm偏移值亦低於149℃，但EVA膜與囊封黏膠之不混溶性之限制導致雜散增加。
實例4
各種熱熔黏膠(1,000g)及封裝膜(以熱熔黏膠計0.5wt%)形成之熱熔黏膠封裝列示於表4。將每一封裝加載於熔化槽，並在無任何攪拌之情況下於所列示溫度下加熱。目測觀察膜在熱熔黏膠中之混溶性。同樣，記錄膜樣品完全溶解並變得於黏膠中混溶所需之時間長度。
如上觀察所知，封裝膜(1)係由包括至少70wt%丙烯含量之聚丙烯共聚物製得；(2)在200℃下之黏度範圍為約200,000cps至3,000,000cps；(3)熔化峰值溫度範圍為約90℃至140℃；(4)Tm偏移溫度低於 149℃；(5)在100℃下之儲存模數(G’)為約1×106帕斯卡至1×108帕斯卡，該封裝膜可與各種聚合物形成之各種及多種熱熔黏膠混溶，且可用作整合性熱熔黏膠封裝之通用封裝黏膠。

Claims (20)

  1. 一種包括聚合物摻合物之熱熔封裝膜，其中該聚合物摻合物包括至少70wt%之丙烯含量；及其中該封裝膜具有(a)在200℃下約200,000cps至3,000,000cps之黏度範圍；(b)約90℃至140℃之峰值熔化溫度範圍；(c)低於149℃之Tm偏移溫度；及(d)在100℃下約1×106帕斯卡至約1×108帕斯卡之儲存模數(G’)範圍。
  2. 如請求項1之封裝膜，其進一步包括選自由以下組成之群之添加劑：抗結塊劑、抗氧化劑、流動調節劑、填料、染料及其混合物。
  3. 如請求項1之封裝膜，其中該聚合物摻合物中之至少一種聚合物係茂金屬催化之聚丙烯聚合物。
  4. 如請求項1之封裝膜，其中該聚合物摻合物包括乙烯及/或丁烯共聚單體。
  5. 如請求項4之封裝膜，其中該聚合物摻合物包括：a.約70wt%至約99wt%之丙烯含量；b.約1wt%至約30wt%之乙烯及/或丁烯含量。
  6. 一種物件，其包括如請求項1之封裝膜。
  7. 如請求項6之物件，其係熱熔黏膠封裝。
  8. 如請求項7之物件，其係呈枕狀、圓柱狀、袋狀、塊狀、筒狀或鰷魚狀(chub)。
  9. 一種整合性熱熔黏膠封裝，其包括：(a)熱熔黏膠，其選自由下列組成之群：聚-α-烯烴、橡膠、苯乙烯嵌段共聚物、乙烯-乙酸乙烯酯、乙烯-乙酸丁酯及其混合物；及 (b)封裝膜，其包括包含至少70wt%丙烯之聚合物摻合物；且其中該封裝膜具有(a)在200℃下約200,000cps至3,000,000cps之黏度範圍；(b)約90℃至140℃之峰值熔化溫度範圍；(c)低於149℃之Tm偏移溫度；及(d)在100℃下約1×106帕斯卡至約1×108帕斯卡之儲存模數(G’)範圍；其中該封裝膜以該熱熔黏膠封裝之總重量計係以約0.2%至約2%存在於該熱熔黏膠封裝中；且其中在溫度為149℃或更高時，該封裝膜100%混溶於該熱熔黏膠中而無需任何攪拌。
  10. 如請求項9之整合性熱熔黏膠封裝，其中該封裝膜進一步包括選自由以下組成之群之添加劑：抗結塊劑、抗氧化劑、流動調節劑、填料、染料及其混合物。
  11. 如請求項9之整合性熱熔黏膠封裝，其中該聚合物摻合物之至少一種聚合物係茂金屬催化之聚丙烯聚合物。
  12. 如請求項11之整合性熱熔黏膠封裝，其中該聚合物摻合物包括乙烯及/或丁烯共聚單體。
  13. 如請求項11之整合性熱熔黏膠封裝，其中該聚合物摻合物包括：a.約70wt%至約99wt%之丙烯含量；b.約1wt%至約30wt%之乙烯及/或丁烯含量。
  14. 如請求項9之整合性熱熔黏膠封裝，其中該熱熔黏膠係基於聚-α-烯烴、烯烴嵌段共聚物或苯乙烯嵌段共聚物之黏膠。
  15. 如請求項9之整合性熱熔黏膠封裝，其包括厚度為約0.5mil至約5mil之單層封裝膜。
  16. 如請求項9之整合性熱熔黏膠封裝，其包括多層封裝膜，其中每一層之厚度為約0.5mil至約5mil。
  17. 如請求項9之整合性熱熔黏膠封裝，其形成為枕狀、圓柱狀、袋 狀、塊狀、筒狀或鰷魚狀。
  18. 一種形成整合性熱熔黏膠封裝之方法，其包括以下步驟：1.製備用作囊封容器之封裝膜；2.將熔化態之熱熔黏膠泵送或傾倒於該封裝膜中，其中該封裝膜與散熱器直接接觸；3.密封該封裝膜；及4.冷卻該密封之封裝；且其中該封裝膜包括包含至少70wt%丙烯之聚合物摻合物；且該封裝膜具有(a)在200℃下約200,000cps至3,000,000cps之黏度範圍；(b)約90℃至140℃之峰值熔化溫度範圍；(c)低於149℃之Tm偏移溫度；及(d)在100℃下約1×106帕斯卡至約1×108帕斯卡之儲存模數(G’)；其中該熱熔黏膠係選自由下列組成之群：聚-α-烯烴、橡膠、苯乙烯嵌段共聚物、乙烯-乙酸乙烯酯、乙烯-乙酸丁酯及其混合物；且其中該冷卻之密封封裝無黏性。
  19. 如請求項18之形成整合性熱熔黏膠封裝之方法，其中泵送或傾倒該熔化態熱熔黏膠係在約150℃或更低之溫度下實施。
  20. 如請求項18之形成整合性熱熔黏膠封裝之方法，其中該散熱器係水。
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