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TWI521032B - 濕性膠 - Google Patents

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TWI521032B
TWI521032B TW102120482A TW102120482A TWI521032B TW I521032 B TWI521032 B TW I521032B TW 102120482 A TW102120482 A TW 102120482A TW 102120482 A TW102120482 A TW 102120482A TW I521032 B TWI521032 B TW I521032B
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娜塔莎 齊索夫斯基
伊莎貝爾 尤爾
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羅門哈斯公司
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Description

濕性膠
本發明係關於一種水性黏著劑組成物，通常係習知為濕性膠黏著劑。更具體而言，本發明係關於水性黏著劑組成物，其包括：a)一種乳化聚合物，係包含，作為共聚合單元，以該乳化聚合物之重量為基準計，自10重量%至35重量%之羧酸單體，以及至少一種第二乙烯系不飽和單體；以及b)以該乳化聚合物之重量為基準計，自0.1重量%至4重量%之環氧矽烷；其中，該黏著劑組成物係實質上不含交聯劑。本發明亦關於一種用於提供擔載可移除紙標籤之基板的方法，以及自擔載可移除標籤基板移除紙標籤的方法。
基於鹼可溶脹性丙烯酸系聚合物的濕性膠黏著劑，在紙標籤的應用上，通常施用於玻璃飲料瓶上。當置於冰水浴中時，該標籤必須黏附於該瓶，更須在使用典型高溫及苛性溶液之回收操作中可輕易移除之。基於此化學性之濕性膠組成物顯現不良之抗冰浴性及需要，舉例而言，加入天然產物如酪蛋白或澱粉以改良抗性。
美國專利申請案公開第20010021452號揭露 了自丙烯酸系聚合物、矽烷耦合劑、及具有一定溶膠及凝膠含量的交聯劑所形成之壓敏感黏著劑。在標籤應用中，仍需要具有抗冰水性與可移除性取得所欲平衡的黏著劑組成物。本發明黏著劑組成物提供此特性之平衡。
於本發明之第一態樣，係提供一種水性黏著劑組成物，其係包含：a)一種乳化聚合物，係包含，作為共聚合單元，以該乳化聚合物之重量為基準計，自10重量%至35重量%之羧酸單體，以及至少一種第二乙烯系不飽和單體；以及b)以該乳化聚合物之乾重為基準計，自0.1重量%至4重量%之環氧矽烷；其中，該黏著劑組成物係實質上不含交聯劑。
於本發明之第二態樣，係提供一種用於提供擔載可移除紙標籤之基板的方法，其係包含(a)形成本發明之第一態樣之水性黏著劑組成物；(b)將該水性黏著劑組成物施用至該紙標籤上；以及(c)將該擔載有黏著劑之標籤施用至該基板上。
於本發明之第三態樣，係提供一種自擔載有可移除紙標籤之基板移除紙標籤的方法，其係包含：(a)提供本發明之第二態樣之擔載有可移除紙標籤的基板；以及(b)將該可移除標籤與鹼性溶液於足以移除該標籤之溫度接觸一段時間。
本發明係關於一種水性黏著劑組成物。本文中，「水性組成物」意指水以及以該介質之重量為基準計，自0重量%至30重量%之可與水互溶的化合物。
該水性黏著劑組成物，或者水性紙標籤黏著劑組成物，係包括一種乳化聚合物，其係包含，作為共聚合單元，以該乳化聚合物之重量為基準計，自10重量%至35重量%，較佳自15重量%至30重量%之羧酸單體以及至少一種第二乙烯系不飽和單體。此乳化聚合物係落在通常意指為鹼可溶脹聚合物之範疇。適宜之羧酸單體包括，舉例而言，丙烯酸、甲基丙烯酸、巴豆酸、伊康酸、富馬酸、馬來酸、伊康酸單甲酯、富馬酸單甲酯、富馬酸單丁酯、及馬來酸酐。較佳之羧酸單體係(甲基)丙烯酸。
該至少一種共聚合第二單乙烯系不飽和單體排除羧酸單體，其係包括，舉例而言，(甲基)丙烯酸系酯單體，包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、脲基官能性(甲基)丙烯酸酯類及(甲基)丙烯酸之乙醯乙酸酯類、乙醯胺類或氰乙酸酯類；苯乙烯或經取代之苯乙烯；乙烯基甲苯；丁二烯；乙酸乙烯酯或其他乙烯基酯類；乙烯基單體如氯乙烯、偏氯乙烯(vinylidene chloride)、N-乙烯基吡咯烷酮；(甲基)丙烯腈；以及N-羥烷基(甲基)丙烯醯胺。在本說明書中，使用術語「(甲基)」後綴有另一術 語者，如(甲基)丙烯酸酯或(甲基)丙烯醯胺係分別意指丙烯酸酯或丙烯醯胺與甲基丙烯酸酯及甲基丙烯醯胺兩者。骨架主要為丙烯酸系或苯乙烯-丙烯酸系組成物者，為較佳之聚合物。
視需要，低含量之多乙烯系不飽和單體如，舉例而言，(甲基)丙烯酸烯丙酯、鄰苯二甲酸二烯丙酯、丁二烯、1,4-丁二醇二(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯及二乙烯基苯可包含於該乳化聚合物中。預期使用例如自0%至0.5%含量的多乙烯系不飽和單體，但必須經選擇以不損害該組成物之黏著特性。
典型用於形成本發明之第一聚合物方法的乳液聚合技術係該技術領域中習知者，例如，舉例而言，於美國專利第4,325,856號、第4,654,397號及第4,814,373號中所揭露者。可使用傳統之界面活性劑例如，舉例而言，陰離子及/或非離子乳化劑例如，舉例而言，鹼金屬、或銨、烷基、或乙氧基化烷基、硫酸酯、烷基磺酸、脂肪酸、磷酸鹽界面活性劑例如，舉例而言，RHODOFACTM RS-610及RHODOFACTM RS-960以及氧乙基化烷基酚類。所使用之界面活性劑的含量通常為，以總單體之重量為基準計，0.1重量%至6重量%。可使用熱起始製程或氧化還原起始製程。可使用傳統之自由基起始劑，亦意指為觸媒，例如，舉例而言，過氧化氫、第三丁基過氧化氫、第三戊基過氧化氫、過硫酸銨及/或鹼性過硫酸鹽，其含量典型為，以總 單體之重量為基準計，0.01重量%至3.0重量%。其氧化還原系統係使用相同起始劑，並偶合適宜之相似含量之還原劑(亦指活化劑)(例如，舉例而言，甲醛次硫酸鈉、亞硫酸氫鈉、異抗壞血酸、硫酸羥胺及重亞硫酸鈉)，其視需要與金屬離子例如，舉例而言，鐵及銅合用，視需要進一步包括該金屬用之錯合劑。可使用鏈轉移劑例如硫醇以降低該聚合物之分子量。
該單體可單獨加入或以單體混合物形式加入；其可以純物形式加入或作為水乳液而加入。於某些具體實施例中，該單體係於兩個或更多個階段中加入。
可採用產生多峰粒徑(polymodel particle size)分佈之製程，例如，舉例而言，該等於美國專利第4,384,056號及第4,539,361號中所揭露者。
該藉由布魯克海文儀器公司(Brookhaven Instrument Corp.,Holtsville,NY)提供之Brookhaven Model BI-90型粒徑儀量測之水性乳化聚合物顆粒之平均顆粒直徑典型係，自30nm至500nm，較佳自75nm至300nm，且更佳自90nm至250nm。
本發明之水性黏著劑組成物包括，以該乳化聚合物之乾燥重量為基準計，自0.1重量%至4重量%，較佳自1.5重量%至3.0重量%之環氧矽烷。本文中，「環氧矽烷」包括環氧丙氧基烷基三甲氧基矽烷。較佳係3-環氧丙氧基丙基三甲氧基矽烷。
該水性黏著劑組成物之pH典型係自3至11 之範圍，較佳係自6至10之範圍。該水性黏著劑組成物之任意pH調整較佳係以氨作用之。該水性黏著劑組成物之適宜黏度範圍係自50,000cps至120,000cps(布魯克菲爾德(Brookfield)黏度，RVT轉軸7，速度為20rpm)，較佳自80,000caps至120,000cps。
該水性黏著劑組成物除了含有該乳化聚合物之外，可含有其量為本發明之該第一聚合物之0重量%至200重量%的成膜或非成膜溶液或第二乳化聚合物，例如，舉例而言，尿素及來自植物源或動物源之天然產物以及自其衍生之材質，例如，舉例而言，澱粉及酪蛋白。若視需要之第二乳化聚合物為乳化聚合物，包括，作為共聚合單元，以該乳化聚合物之重量為基準計，自10重量%至35重量%之羧酸單體及至少一種第二乙烯系不飽和單體，則羧酸之含量係基於該乳化聚合物之整體組成而計算之。其他成份包括視需要之有機或無機顏料或增量劑，以及傳統之佐劑，例如，舉例而言，乳化劑、聚結劑、塑化劑、抗凍劑、緩衝劑、中和劑、增稠劑、光敏成份、流變修飾劑、保濕劑、潤濕劑、殺生物劑、塑化劑、抗發泡劑、UV吸收劑、螢光增亮劑、光或熱安定劑、殺生物劑、螯合劑、分散劑、著色劑、防水劑及抗氧化劑。
該水性黏著劑組成物係實質上不含交聯劑，亦即，實質上不含能夠交聯該乳化聚合物之獨立化合物或組成物。該水性黏著劑組成物之環氧矽烷成分係明確地被排除於本文之「交聯劑」中。本文中，「實質上不含交 聯劑」係意指，以該乳化聚合物之乾燥重量為基準計，交聯劑之含量係低於0.001重量份(parts)。本文中，「交聯劑」包括多官能三聚氰胺化合物、多官能環氧化合物、多官能異氰酸酯化合物等。
於本發明之用於提供擔載有可移除紙標籤之基板的方法中，該黏著劑組成物係施用於紙標籤上。本文中，「紙標籤」包括由任何各種形式的紙、經塗覆之紙、印刷紙、擔載有金屬塗層或金屬箔之紙製成的標籤。可使用傳統之濕性黏著劑應用方法。該紙標籤上之該水性黏著劑組成物可有助於施用至基板，例如，舉例而言，玻璃及聚合性材質上。典型係於室溫條件，例如，舉例而言，0℃至35℃，進行乾燥。
於自擔載有可移除紙標籤之基板移除紙標籤的方法中，該可移除標籤係與鹼性溶劑於足以移除該標籤之溫度接觸一段時間。本文中，「可移除性」係藉由在下文實驗測試方法中所詳述之「洗除測試」的結果判定。
[實施例]
實驗測試方法
抗冰水性
以梅耶爾棒(Meyer bar)將濕性黏著劑以5至8g/m2之乾燥含量施用至標籤上。使用尺寸為60×80毫米(mm)之標籤。
將黏附於玻璃瓶上之該標籤於室溫存儲4天。於存儲之後，將該瓶裝滿水並浸沒於冰水浴中。記錄 直到該標籤脫落之時間。於此測試中，5天或大於5天之數值係歸為通過。
洗除測試
此測試過程係用於測試黏著劑於熱鹼性水溶液中的脫落能力。
「洗除能力」係黏著劑於65至75℃之1.0至2.0%氫氧化鈉溶液中自行快速且完全脫落的能力。
使用尺寸為60×80mm之標籤。
將黏附於玻璃瓶上之該標籤於標準氣候條件(23℃±2℃、50% RH±5% RH)存儲至少24小時。於存儲之後，將該瓶於測試溫度裝滿水，並立即浸沒於測試溫度之氫氧化鈉溶液中。
記錄直到該標籤脫落之時間以及於標籤已脫落之後該黏著劑的位置。此測試中，5分鐘或小於5分鐘之數值係歸為通過。
下述實施例係用以例示性說明本發明。
所使用之縮寫
水性乳化聚合物之組成(以重量為基準計)：乳化聚合物A=p(50 EA/3 Sty/25 MMA/18 MAA)乳化聚合物B=p(80 EA/20 MAA)乳化聚合物C=p(62 BMA/38 MAA)乳化聚合物D=p(56EA/5EHA/36MAA)
實施例1至2及比較例A至B：水性黏著劑組成物之配製及評估
使用第3號棒將該水性黏著劑組成物以24g/m2之濕性含量施用至紙標籤上，並於室溫乾燥4天。
SILQUESTTM A-187係來自Momentive Specialty Chemicals Inc.(Columbus,OH)之環氧官能性矽烷。
本發明之實施例1至2之水性黏著劑組成物顯現所欲水準之抗冰水性及洗除效能。

Claims (3)

  1. 一種水性黏著劑組成物，其包含：a)一種乳化聚合物，包含，作為共聚合單元，以該乳化聚合物之重量為基準計，自10重量%至35重量%之羧酸單體，以及至少一種選自下列所組成群組之乙烯系不飽和單體：(甲基)丙烯酸系酯、苯乙烯、經取代之苯乙烯、乙烯基甲苯、丁二烯、乙烯基酯、氯乙烯、偏氯乙烯、N-乙烯基吡咯烷酮、(甲基)丙烯腈以及N-羥烷基(甲基)丙烯醯胺；以及b)以該乳化聚合物之乾重為基準計，自0.1重量%至4重量%之環氧矽烷；其中，該黏著劑組成物係實質上不含交聯劑。
  2. 一種用於提供擔載可移除紙標籤之基板的方法，其包含：(a)形成如申請專利範圍第1項所述之水性黏著劑組成物；(b)將該水性黏著劑組成物施用於紙標籤；(c)將所施用之黏著劑組成物乾燥或讓其乾燥；以及(d)將該擔載黏著劑之標籤施用於該基板。
  3. 一種自擔載有可移除紙標籤之基板移除紙標籤的方法，其包含：(a)提供如申請專利範圍第2項所述之擔載有可移除紙標籤的基板；以及(b)將該可移除標籤與鹼性溶液於足以移除該標籤之 溫度接觸一段時間。
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